Curable Composition

ABSTRACT

Firstly, disclosed is a curable composition which includes an organic polymer containing a crosslinkable silyl group, an ultraviolet ray absorbing agent having a triazine skeleton and a hindered amine based light stabilizer, and thereby, exhibits improved weather resistance both in a thin layer portion and in a thick layer portion. Secondly, disclosed is a curable composition which includes an organic polymer containing a crosslinkable silyl group, a (meth)acrylic polymer containing an epoxy group, a divalent tin organic carboxylate and an organic amine compound, and thereby, exhibits excellent weather resistance, anti-staining property, restoring property and durability. Thirdly, disclosed are an excellent curable composition which includes a reactive organic polymer containing at least one crosslinkable silyl group in one molecule thereof, a reactive organic polymer containing less than one crosslinkable silyl group in one molecule thereof, and thermally expandable hollow spheres as essential components, and thereby, exhibits economical productivity, good physical properties, safety and fire resistance; and a sealing material produced from the curable composition. Further, disclosed is a method for forming a fire-resistant structure with ease and at a low cost.

TECHNICAL FIELD

The present invention firstly relates to a curable composition excellentin weather resistance, and a sealing material using the curablecomposition as an available ingredient and excellent in weatherresistance. The present invention secondly relates to a curablecomposition excellent in restoring property, durability, weatherresistance, and paint anti-staining property, and a sealing materialusing the curable composition as an available ingredient. The presentinvention thirdly relates to a curable composition excellent in fireresistance, a sealing material using the curable composition as anavailable ingredient and having fire resistance, and a method of forminga fire-resistant structure involving the use of the sealing material.

BACKGROUND ART

A sealing material has been conventionally blended with a stabilizer inorder that weather resistance may be imparted to the material. However,irrespective of the above fact, such whitening problems as describedbelow occur, and have been serious problems to be solved in the field ofsealing material construction. One of the whitening problems is asdescribed below. When a masking tape is stuck on a portion apart from ajoint of an adherend due to an error in construction at the time of theplacement of the sealing material, thin layer parts are formed afterspatulation for flattening the surface of the sealing material at ajoint portion, and the thin layer parts each deteriorate to whiten morequickly than the sealing material at the joint portion, with the resultthat the appearance of a structure becomes poor, and the design of thestructure becomes extremely bad.

At present, there is no technology for solving the whitening phenomenonof those thin layer parts (hereinafter collectively referred to as “thinlayer portion”). Details about the foregoing are as described below.Conventionally known examples of a stabilizer having good weatherresistance to be blended into the sealing material include a combinationof a benzotriazole based ultraviolet ray absorbing agent and a hinderedphenol based antioxidant as described in Patent Document 1, acombination of a benzotriazole based ultraviolet ray absorbing agent anda specific hindered amine based light stabilizer as described in PatentDocument 2, and a combination of a benzotriazole based ultraviolet rayabsorbing agent and a hindered amine based light stabilizer containing aspecific triazine skeleton as described in Patent Document 3. Thosestabilizers are effective for, for example, sealing materials at thick(for example, 5 mm or more in thickness) joint portions (hereinaftercollectively referred to as “thick layer portion”), but none of thosestabilizers is effective for the thin layer portion, and no stabilizerformulation capable of improving the weather resistance of the thinlayer portion and that of the thick layer portion simultaneously isknown.

In view of the foregoing, in the field of sealing materials, there is ademand for a sealing material designed so that a thin layer portion isprevented from deteriorating to whiten more quickly than a thick layerportion, and, at the same time, the thick layer portion exerts excellentweather resistance. Patent Document 4 describes that a combination of abenzotriazole based ultraviolet ray absorbing agent, a hindered aminebased compound having a molecular weight of 200 to 1,000 and free of atriazine skeleton in any one of its molecules, and a hindered aminecompound having a triazine skeleton in any one of its molecules as lightstabilizers is a stabilizer formulation having good weather resistancein each of a thin layer portion, and a thick layer portion. However, itcannot yet be said that the weather resistance is sufficient.

In addition, an oxypropylene polymer having a crosslinkable silyl groupcapable of curing into a rubber-like substance by virtue of moisture orthe like has been conventionally utilized, for example, in an elasticsealant for structures or the like. In this case, a composition obtainedby blending the polymer with a plasticizer, a filler, and the like hasbeen utilized in terms of physical properties and of cost. The restoringproperty of the sealant for filling a joint of the structure plays animportant role in following the fluctuation of the joint due to ahumidity difference.

Various investigations have been conducted on a curable compositionexcellent in restoring property (see, for example, Patent Documents 5and 6). However, the physical properties of the composition such asweather resistance and paint anti-staining property have been poor.

Further, a curable resin composition having fire resistance has beencurrently produced on an industrial scale, and has been finding use in awide variety of fields including structure-, automobile-, and electricmachinery-related fields. In particular, in a sealing materialapplication, a sealing material superior in fire resistance compared toa conventional one has been requested in association with the recentincrease of interest in safety.

Sealing materials each containing a polyphosphate compound as a foamingagent have been known as examples of fire resistant sealing materialsthat have already been on the market. Of the materials, a materialcontaining ammonium polyphosphate is effective; the generation of anammonia gas caused by the hydrolysis of the material and phosphorus inthe material promote the carbonization of any other substance to causethe substance to produce an incombustible carbonized layer, whereby thematerial has fire resistance (see, for example, Patent Documents 7 and8).

However, none of the sealing materials each containing a polyphosphatecompound can obtain predetermined fire resistance unless the loading ofthe polyphosphate compound is equal to or higher than a certain level.Moreover, blending each of the sealing materials with the polyphosphatecompound involves the following problems: reductions in physicalproperties of each of the sealing materials and an increase in cost forthe production of each of the sealing materials.

In addition, a sealing material obtained by adding a foaming agent to avinyl based organic polymer has been known as examples of any othersealing material having fire resistance; the material is formed on thebasis of the vinyl based organic polymer having good heat resistance,and the foaming agent in the material expands or generates a gas to forma foaming layer having heat insulating property, whereby the materialhas fire resistance (see, for example, Patent Document 9).

However, the vinyl based organic polymer is inherently poor inelongation property. In addition, blending the vinyl based organicpolymer with the foaming agent involves the following problem:additional reductions in the physical properties of the polymer.

In addition, from the viewpoint of fire resistance, a method of making apart other than a sealing material (mainly a back-up material)fire-resistant has been employed for the purpose of imparting fireresistance to a joint portion. To be specific, the following method hasbeen known: a foaming asbestos body cut to be adjusted to be the widthof a joint (for example, trade name “Litoflex” manufactured by NICHIASCorporation) is inserted under pressure into the bottom of the joint,and, furthermore, an ordinary sealing material is loaded into the upperportion of the resultant, whereby compatibility between fire resistanceand water resistance is achieved.

However, such method must be executed by an expert in order that fireresistance may not vary from place to place, and requires the followingcomplicated operation: the body must be cut to be adjusted to be a jointshape that varies from place to place. As a result, the method isextremely costly.

A silicone based sealing material different from the present inventionin composition has also been attracting attention because of itsexcellent flame resistance. However, the material involves the followingproblems: the material is poor in coating property, and causeswater-repellent staining.

Patent Document 1: JP 5-287186 A

Patent Document 2: JP61-233043A

Patent Document 3: JP8-48888A

Patent Document 4: JP2001-271057A

Patent Document 5: JP55-9669A

Patent Document 6: JP01-29821B

Patent Document 7: JP2832222B

Patent Document 8: JP8-253761A

Patent Document 9: JP2001-354830A

DISCLOSURE OF THE INVENTION Problems to be solved by the Invention

A first object of the present invention is to provide a curablecomposition and a sealing material each having improved weatherresistance in each of a thin layer portion and a thick layer portion. Asecond object of the present invention is to provide a curablecomposition and a sealing material each of which are excellent inweather resistance, paint anti-staining property, restoring property,and durability. A third object of the present invention is to provide anexcellent curable composition and an excellent sealing material eachhaving economical productivity, good physical properties, safety, andfire resistance. Another object of the present invention is to provide amethod of forming a fire-resistant structure with ease at a low cost.

Means for solving the Problems

To solve the above-mentioned problems, according to a first aspect of acurable composition of the present invention, the curable compositioncomprises: (A) an organic polymer containing a crosslinkable silylgroup; (B) an ultraviolet ray absorbing agent having a triazineskeleton; and (C) a hindered amine based light stabilizer. A curablecomposition having improved weather resistance in each of a thin layerportion and a thick layer portion can be obtained from the curablecomposition of the present invention.

(A) The organic polymer containing a crosslinkable silyl group ispreferably one or more kinds of compounds selected from the groupconsisting of a polyoxyalkylene based polymer containing a crosslinkablesilyl group, a (meth)acrylic-modified polyoxyalkylene based polymercontaining a crosslinkable silyl group, and a (meth)acrylic polymercontaining a crosslinkable silyl group, or is more preferably a(meth)acrylic polymer having a crosslinkable silyl group at a terminalof its molecular chain, or the mixture of the (meth)acrylic polymerhaving a crosslinkable silyl group at a terminal of its molecular chainand a polyoxyalkylene based polymer containing a crosslinkable silylgroup. It should be noted that the terms “acrylic” and “methacrylic” arecollectively referred to as “(meth)acrylic” in the present invention.

A method of producing the (meth)acrylic polymer having a crosslinkablesilyl group at a terminal is not particularly limited; a controlledradical polymerization method is preferable, a living radicalpolymerization method is more preferable, and an atom transfer radicalpolymerization method is still more preferable.

In the first aspect of the curable composition of the present invention,the curable composition suitably further contains (D) a compound thatreacts with water to produce an amine compound. Thus, a curablecomposition excellent in anti-staining property as well as weatherresistance can be obtained.

As (C) the hindered amine based light stabilizer, a hindered amine basedcompound having a triazine skeleton or a hindered amine based compoundfree of a triazine skeleton may be used. In addition, as (C) thehindered amine based light stabilizer, a mixture of a hindered aminebased compound having a triazine skeleton and a hindered amine basedcompound free of a triazine skeleton may be used.

According to a first aspect of a sealing material of the presentinvention, the sealing material comprises the first aspect of thecurable composition of the present invention as an available ingredient,and has excellent weather resistance.

According to a second aspect of a curable composition of the presentinvention, the curable composition comprises: (E) an organic polymercontaining a crosslinkable silyl group; (F) a (meth)acrylic polymercontaining an epoxy group; (G) a divalent tin organic carboxylate; and(H) an organic amine compound. A curable composition excellent inweather resistance, paint anti-staining property, restoring property,and durability can be obtained from the curable composition of thepresent invention.

(E) The organic polymer containing a crosslinkable silyl group ispreferably a (meth)acrylic polymer containing a crosslinkable silylgroup. The (meth)acrylic polymer containing a crosslinkable silyl groupis preferably a (meth)acrylic organic polymer having a crosslinkablesilyl group at a terminal of its molecular chain, or the mixture of the(meth)acrylic polymer having a crosslinkable silyl group at a terminalof its molecular chain and an organic polymer containing a crosslinkablesilyl group. A method of producing the (meth)acrylic polymer having acrosslinkable silyl group at a terminal is not particularly limited; acontrolled radical polymerization method is preferable, a living radicalpolymerization method is more preferable, and an atom transfer radicalpolymerization method is still more preferable.

(F) the (meth)acrylic polymer containing an epoxy group has a weightaverage molecular weight within the range of preferably 1,000 to 7,500.

According to a second aspect of a sealing material of the presentinvention, the sealing material comprises the second aspect of thecurable composition of the present invention as an available ingredient,and is excellent in weather resistance, paint anti-staining property,restoring property, and durability.

According to a third aspect of a curable composition of the presentinvention, the curable composition comprises: (I) a reactive organicpolymer containing at least one crosslinkable silyl group in any one ofits molecules; (J) a reactive organic polymer containing less than onecrosslinkable silyl group in any one of its molecules; and (K) thermallyexpandable hollow spheres as essential components, wherein the curablecomposition contains the component (K) in an amount within the range of0.01 part by mass to 20 parts by mass with respect to a total of 100parts by mass of the components (I) and (J). An excellent curablecomposition having economical productivity, good physical properties,safety, and fire resistance can be provided by the curable compositionof the present invention.

(I) The reactive organic polymer containing at least one crosslinkablesilyl group in any one of its molecules is preferably a (meth)acrylicpolymer containing a crosslinkable silyl group. The (meth)acrylicpolymer containing a crosslinkable silyl group is preferably a(meth)acrylic polymer having a crosslinkable silyl group at a terminalof its molecular chain, or the mixture of the (meth)acrylic polymerhaving a crosslinkable silyl group at a terminal of its molecular chainand a polyoxyalkylene based polymer containing a crosslinkable silylgroup.

A method of producing the (meth)acrylic polymer having a crosslinkablesilyl group at a terminal is not particularly limited; a controlledradical polymerization method is preferable, a living radicalpolymerization method is more preferable, and an atom transfer radicalpolymerization method is still more preferable.

(J) The reactive organic polymer containing less than one crosslinkablesilyl group in any one of its molecules is suitably a (meth)acrylicpolymer. In addition, (J) the reactive organic polymer containing lessthan one crosslinkable silyl group in any one of its molecules has aweight average molecular weight of preferably 2,000 to 50,000.

According to the third aspect of the curable composition of the presentinvention, the curable composition contains the component (J) in anamount of preferably 10 to 300 parts by weight with respect to 100 partsby weight of the component (I).

In the third aspect of the curable composition of the present invention,the hardness of a rubber-like elastic body after the curing of thecomposition measured with a rubber hardness meter (JIS A type) ispreferably 40 or less.

According to the third aspect of the sealing material of the presentinvention, the sealing material comprises the third aspect of thecurable composition of the present invention as an available ingredient,and has excellent fire resistance.

A forming method of the present invention comprises forming afire-resistant structure using a wall material having fire resistanceand the sealing material having fire resistance according to the presentinvention.

EFFECT OF THE INVENTION

Firstly, according to the present invention, a curable composition and asealing material each having improved weather resistance in each of athin layer portion and a thick layer portion can be obtained. Further,according to the present invention, a curable composition and a sealingmaterial each of which is excellent in anti-staining property as well asweather resistance and has a high elongation rate can also be obtained.

Secondly, according to the present invention, a curable compositionwhich is excellent in weather resistance, paint anti-staining property,restoring property, and durability and which is suitably usedparticularly in, for example, a sealing material for the structure canbe obtained. In addition, according to the present invention, a sealingmaterial excellent in weather resistance, paint anti-staining property,restoring property, and durability can be obtained. Further, accordingto the present invention, in addition to the above effects, there can beobtained a curable composition which has a high elongation rate and issuitably used in a sealing material, and a sealing material having ahigh elongation rate.

Thirdly, according to the present invention, there can be provided anexcellent curable composition which has economical productivity, goodphysical properties, safety, and fire resistance. Further, according tothe present invention, a curable composition having a high elongationrate as well as the above effects can be obtained. The third aspect ofthe curable composition of the present invention is most suitably usedin a sealing material; the composition can be used in, for example, anadhesive, a pressure-sensitive adhesive, a coating material, or apotting material as long as the composition is used in applicationswhere fire resistance is expected from the composition. The sealingmaterial having fire resistance of the present invention exerts thefollowing significant effects: the sealing material maintains goodphysical properties, has high cost performance, can be applied, does notcause water-repellent staining, and can be turned into a one-componentliquid. Furthermore, the sealing material forms a foaming heatinsulating layer when exposed to flame to shield, for example, heat,flame, smoke, and a gas generated by combustion. According to theformation method of the present invention, a fire-resistant structurecan be formed with ease at a low cost.

Any one of the first to third aspects of the curable composition of thepresent invention is particularly suitably used in a sealing material;any one of the aspects can be used in, for example, an adhesive, apressure-sensitive adhesive, a coating material, or a potting material.The curable composition of the present invention can be used for, forexample, various structures, automobiles, civil engineering, andelectrical and electronic fields.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic explanatory view showing an example of afire-resistant structure to be formed by a formation method of thepresent invention.

FIG. 2 is a top view of FIG. 1.

DESCRIPTION OF REFERENCE NUMERALS

10, 11: wall materials, 12: a sealing material, 13: a fire-resistantstructure, 14: a filler, A: an abutting portion

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, an embodiment of the present invention will be describedwith reference to the attached drawings. Needless to say, however, theshown examples are merely exemplary, and various modifications can bemade without departing from the technical idea of the present invention.

The first aspect of the curable composition of the present inventioncomprises the following components (A), (B) and (C):

(A) an organic polymer containing a crosslinkable silyl group;

(B) an ultraviolet ray absorbing agent having a triazine skeleton; and

(C) a hindered amine based light stabilizer.

An organic polymer containing a silicon-containing group having ahydroxyl group or a hydrolyzable group bonded to a silicon atom andcapable of crosslinking by the formation of a siloxane bond, that is, acrosslinkable silyl group is used as the component (A). Examples of suchan organic polymer containing crosslinkable silyl group-containing (A)include those disclosed in JP5-287186A, JP61-233043A, JP1-58219B,JP3062625B, JP8-337713A, JP2003-138151A, JP11-12480A, JP52-73998A,JP55-9669A, JP59-122541A, JP60-6747A, JP63-112642A, JP03-79627A,JP04-283259A, JP05-70531A, JP11-80571A, JP11-116763A, JP11-130931A,JP2001-40037A, JP3313360B, JP2004-51830A, JP2004-59782A, JP2001-329065A,and JP2001-271055A. Specific examples of the organic polymer containinga crosslinkable silyl group (A) include a polyoxyalkylene based polymer,a vinyl-modified polyoxyalkylene based polymer, a vinyl based polymer, apolyester polymer, and a (meth)acrylate polymer each of which contains acrosslinkable silyl group and the main chain of each of which maycontain organosiloxane, and a copolymer or mixture of two or more ofthem.

One molecule of the polymer generally contains 1 to 6 crosslinkablesilyl groups in terms of, for example, the curing property of thecomposition and the physical properties of the composition after thecuring of the composition, though the number of the groups is notparticularly limited. Further, the crosslinkable silyl group ispreferably a group represented by the following general formula (1)because the group can be easily crosslinked, and can be easily produced:

[where R¹ represents a substituted or unsubstituted, monovalent organicgroup having 1 to 20 carbon atoms, preferably represents an alkyl grouphaving 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,or an aralkyl group having 7 to 20 carbon atoms, or most preferablyrepresents a methyl group, and, when multiple R¹'s are present, themultiple R¹'s may be identical to or different from each other, Xrepresents a hydroxyl group or a hydrolyzable group, preferablyrepresents a group selected from a halogen atom, a hydrogen atom, ahydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group,an amide group, an acid amide group, a mercapto group, an alkenyloxygroup, and an aminooxy group, more preferably represents an alkoxygroup, or most preferably represents a methoxy group, and, when multipleX's are present, the multiple X's may be identical to or different fromeach other, and a represents 1, 2, or 3, or most preferably represents2.]

When multiple crosslinkable silyl groups are present in the organicpolymer containing a crosslinkable silyl group (A), the groups may beidentical to or different from each other. Further, the numbers of a inthe formula (1) may be identical to or different from each other. Inaddition, two or more kinds of organic polymers containing differentcrosslinkable silyl groups may be used.

The main chain of the organic polymer containing a crosslinkable silylgroup (A) is preferably, for example, a polyoxyalkylene based polymer,(meth)acrylic-modified polyoxyalkylene polymer, or (meth)acrylic polymerwhich may contain organosiloxane, or a copolymer or mixture of two ormore of them in terms of physical properties such as tensile strengthand modulus after the curing of the composition.

In addition, the organic polymer containing a crosslinkable silyl group(A) is particularly preferably a vinyl based polymer having acrosslinkable silyl group at a terminal, or is more preferably a(meth)acrylic polymer having a crosslinkable silyl group at a terminal,or the mixture of the (meth)acrylic polymer having a crosslinkable silylgroup and a polyoxyalkylene based polymer having a crosslinkable silylgroup. The use of the (meth)acrylic polymer having a crosslinkable silylgroup at a terminal of any one of its molecules as the component (A) canachieve a high elongation rate particularly useful in a sealingmaterial.

A method of producing the organic polymer containing a crosslinkablesilyl group (A) is not particularly limited, and a known synthesismethod can be utilized. When a polymer which contains a crosslinkablesilyl group and the main chain of which is a vinyl based polymer such asan acrylic polymer is used as the organic polymer containing acrosslinkable silyl group, a vinyl based polymer synthesized by aradical polymerization method is preferably used.

The radical polymerization methods are classified into a general radicalpolymerization method involving merely copolymerizing a monomer having aspecific functional group and a vinyl based monomer by using an azobased compound, a peroxide, or the like as a polymerization initiatorand a controlled radical polymerization method by which a specificfunctional group can be introduced to a controlled position such as aterminal. In the present invention, a vinyl based polymer synthesized bythe controlled radical polymerization method is more effective than apolymer synthesized by the former method.

The controlled radical polymerization methods are further classifiedinto a chain transfer agent method by which a vinyl based polymer havinga specific functional group at a terminal can be obtained as a result ofpolymerization using a chain transfer agent having the functional groupand a living radical polymerization method by which a polymerizationgrowth terminal grows without causing a termination reaction or thelike.

The living radical polymerization method is particularly preferablebecause a polymer having an arbitrary molecular weight, a narrowmolecular weight distribution, and a low viscosity can be obtained, anda monomer having a specific functional group can be introduced to anarbitrary position. It should be noted that, in the present invention,living polymerization includes pseudo-living polymerization in which amolecular chain with an inactivated terminal and a molecular chain withan activated terminal grow while they are in an equilibrium state inaddition to polymerization in which a molecular chain grows while aterminal of the chain continues to have activity at all times.

Examples of the living radical polymerization method include: a methodinvolving the use of a cobalt porphyrin complex as disclosed in J. Am.Chem. Soc., 1994, vol. 116, p. 7943; a method involving the use of aradical scavenger such as a nitroxide compound as disclosed inMacromolecules, 1994, vol. 27, p. 7228; and an atom transfer radicalpolymerization (ATRP) method involving polymerizing a vinyl basedmonomer by using an organic halogen compound, a halogenated sulfonylcompound, or the like as an initiator and a transition metal complex asa catalyst as disclosed in J. Am. Chem. Soc., 1995, vol. 117, p. 5614,Macromolecules, 1995, vol. 28, p. 7901, Science, 1996, vol. 272, p. 866,Macromolecules, 1995, vol. 28, p. 1721, WO96/30421, WO97/18247,WO98/01480, WO98/40415, JP9-208616A, or JP8-41117A. The living radicalpolymerization method, which is not particularly limited, is preferablythe atom transfer radical polymerization method. It should be notedthat, in the present invention, the atom transfer radical polymerizationmethod includes a reverse atom transfer radical polymerization method,that is, a method involving causing a general radical initiator such asa peroxide to act on a high oxide state when an ordinary atom transferradical polymerization catalyst generates a radical such as Cu(II′) whenCu(I) is used as a catalyst to produce equilibrium similar to that ofatom transfer radical polymerization as a result of the action (see, forexample, Macromolecules, 1999, vol. 32, p. 2872).

Examples of the chain transfer agent method include: a method involvingthe use of a halogenated hydrocarbon as a chain transfer agent to obtaina polymer having a halogen at a terminal as disclosed in JP4-132706A;and a method involving the use of, for example, a hydroxylgroup-containing mercaptan or a hydroxyl group-containing polysulfide asa chain transfer agent to obtain a polymer having a hydroxyl group at aterminal as disclosed in JP61-271306A, JP2594402B, or JP54-47782A.

Hereinafter, the atom transfer radical polymerization method will bedescribed. An organic halide, in particular, an organic halide having ahighly reactive carbon-halogen bond (such as a carbonyl compound havinga halogen at α-position or a compound having a halogen at a benzylposition), a halogenated sulfonyl compound, or the like is used as aninitiator for the atom transfer radical polymerization method.

In addition, an organic halide or halogenated sulfonyl compound having afunctional group except a functional group for initiating atom transferradical polymerization such as an alkenyl group, a crosslinkable silylgroup, a hydroxyl group, an epoxy group, an amino group, or an amidegroup can also be used as an initiator for the polymerization. In thiscase, a vinyl based polymer having the functional group at one mainchain terminal and the growth terminal structure of the atom transferradical polymerization at the other main chain terminal is synthesized.In the present invention, an organic halide or halogenated sulfonylcompound having a crosslinkable silyl group is preferably used. In thiscase, a polymer having the crosslinkable silyl group at one terminal anda halogen at the other terminal is obtained, and a polymer havingcrosslinkable silyl groups at both terminals can be obtained bysubstituting the halogen terminal.

The vinyl based monomer to be used in the polymerization is notparticularly limited; in the present invention, one or more kinds ofacrylic monomers such as (meth)acrylic acid, a (meth)acrylate,(meth)acrylonitrile, and (meth)acrylamide are preferably used as maincomponents, and a (meth)acrylate such as an alkyl (meth)acrylate or analkoxyalkyl (meth)acrylate is more preferably used as a main component.

The transition metal complex to be used as a polymerization catalyst isnot particularly limited; a metal complex using an element belonging toGroup 7, 8, 9, 10, or 11 in the periodic table as a central metal ispreferable, a complex of zero-valent copper, monovalent copper, divalentruthenium, divalent iron, or divalent nickel is more preferable, and acomplex of copper is particularly preferable.

A monovalent copper compound is, for example, cuprous chloride, cuprousbromide, cuprous iodide, cuprous cyanide, cuprous oxide, or cuprousperchlorate. When the copper compound is used, any one of the ligandssuch as 2,2′-bipyridyl and a derivative of 2,2′-bipyridyl,1,10-phenanthroline and a derivative of 1,10-phenanthroline, andpolyamines such as tetramethylethylene diamine, pentamethyl diethylenetriamine, and hexamethyltris(2-aminoethyl)amine is added to the compoundfor improving the catalytic activity of the compound.

In addition, a tristriphenylphosphine complex of divalent rutheniumchloride [RuCl₂(PPh₃)₃], a bistriphenylphosphine complex of divalentiron [FeCl₂(PPh₃)₂], a bistriphenylphosphine complex of divalent nickel[NiCl₂(PPh₃)₂], and a bistributylphosphine complex of divalent nickel[NiBr₂(PBu₃)₂] are also suitably used as catalysts. When a rutheniumcompound is used as a catalyst, any one of the aluminum alkoxides isadded as an activator.

The polymerization can be performed in the absence of a solvent or inany one of various solvents. The polymerization is performed in thetemperature range of preferably 0 to 200° C., or more preferably roomtemperature to 150° C.

An acrylic polymer having a halogen at a terminal is produced by theradical polymerization of a vinyl based monomer mainly composed of anacrylic monomer using an organic halogen compound, a halogenatedsulfonyl compound, or the like as an initiator and a transition metalcomplex as a catalyst. The (meth)acrylic polymer having a crosslinkablesilyl group at a terminal of its molecular chain to be used in thepresent invention can be obtained by transforming the halogen of theacrylic polymer having the halogen at a terminal into the crosslinkablesilyl group. A method for the transformation is not particularlylimited, and a known method (see, for example, JP11-80571A,JP11-116763A, JP11-130931A, JP2004-51830A, JP2004-59782A,JP2001-329065A, or JP2001-271055A) can be employed.

In the present invention, the organic polymer containing a crosslinkablesilyl group (A) desirably has a number average molecular weight of 1,000or more to 100,000 or less, in particular, 3,000 to 50,000 and a narrowmolecular weight distribution because the viscosity of the polymerbefore the curing of the composition is so low that the polymer can beeasily handled, and the physical properties of the composition after thecuring of the composition such as strength, an elongation rate, and amodulus are suitable. Only one kind of the organic polymer containing acrosslinkable silyl group (A) may be used, or two or more kinds of suchpolymers may be used in combination.

The component (B) is not particularly limited as long as the componentis an ultraviolet ray absorbing agent having a triazine skeleton, andany one of a wide variety of known compounds can be used as thecomponent. Specific suitable examples of the component (B) includetriazine based compounds each represented by the following formula (2):

[where R² to R⁷ each independently represent a hydrogen atom, a hydroxylgroup, a halogen atom, or a substituted or unsubstituted, monovalentorganic group, or preferably a hydrogen atom, a hydroxyl group, ahalogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkoxygroup having 1 to 18 carbon atoms.]

In particular, a 2-(2-hydroxyphenyl)-1,3,5-triazine based compound inwhich R² in the formula (2) represents a hydrogen atom, a polymerizabletriazine compound represented by the following general formula (3), orthe like is preferable:

[where R³, R⁵, and R⁷ each have the same meaning as that describedabove, or each preferably represent a hydrogen atom or an alkyl grouphaving 1 to 6 carbon atoms, R⁸ represents a hydrogen atom or a methylgroup, and R⁹ represents a substituted or unsubstituted, divalentorganic group, or preferably an alkylene group having 1 to 6 carbonatoms, a —(—CH₂CH₂—O—)_(m) group (m represents an integer of 1 to 5), ora —CH₂CH(OH)—CH₂O— group.]

Examples of the 2-(2-hydroxyphenyl)-1,3,5-triazine-based compoundinclude 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxyl-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine representedby the following formula (4),

2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-methoxyphenyl)-4-(2-hydroxyphenyl)-6-phenyl-1,3,5-triazinerepresented by the following formula (5),

2,4-bis(2-methoxyphenyl)-6-(2-hydroxyphenyl)-1,3,5-triazine representedby the following formula (6),

and compounds represented by the following general formulae (7) and (8).

[where R¹⁰ and R¹¹ each represent a methyl group or an alkoxy grouphaving 1 to 8 carbon atoms, R¹² represents a hydrogen atom, a chlorineatom, a methyl group, or a methoxy group, and R¹³ represents an alkoxygroup having 1 to 8 carbon atoms, and R¹⁴ represents a hydrogen atom ora methoxy group.]

[where R¹⁴ represents the same as described above, and R¹⁵ represents ahydrogen atom or a methyl group.]

Examples of the polymerizable triazine compound include2,4-diphenyl-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine,2,4-diphenyl-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine,2,4-bis(2-methylphenyl)-6-[2-hydroxy-4-(3-acryloyloxy-2-hydroxypropyoxy)]-s-triazine,2,4-bis(2-methoxyphenyl)-6-[2-hydroxy-4-(2-acryloyloxyethoxy)-s-triazine,2,4-bis(2-ethylphenyl)-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine,2,4-bis(2-ethoxyphenyl)-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine,2,4-diphenyl-6-[2-hydroxy-4-(2-methacryloyloxyethoxy)]-s-triazine,2,4-bis(2-methylphenyl)-6-[2-hydroxy-4-(2-methacryloyloxyethoxy)]-s-triazine,2,4-bis(2-methoxyphenyl)-6-[2-hydroxy-4-(2-methacryloyloxyethoxy)]-s-triazine,2,4-bis(2-ethylphenyl)-6-[2-hydroxy-4-(2-methacryloyloxyethoxy)]-s-triazine,2,4-bis(2-ethoxyphenyl)-6-[2-hydroxy-4-(2-methacryloyloxyethoxy)]-s-triazine,2,4-bis(2,4-dimethoxyphenyl)-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine,2,4-bis(2,4-diethoxyphenyl)-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine,and2,4-bis(2,4-diethylphenyl)-6-[2-hydroxy-4-(2-acryloyloxyethoxy)]-s-triazine.

A ratio at which the above component (B) is blended is not particularlylimited; the component is blended in an amount of preferably 0.1 to 50parts by mass, or particularly preferably 1.0 to 10 parts by mass withrespect to 100 parts by mass of the component (A). One kind of the aboveultraviolet ray absorbing agent having a triazine skeleton may be usedalone, or two or more kinds of such agents may be used in combination.

A hindered amine based compound having a triazine skeleton (C1) or ahindered amine based compound free of a triazine skeleton (C2) may beused as the component (C), that is, the hindered amine based lightstabilizer without any particular limitation. Only one kind of suchhindered amine based light stabilizer may be used, or two or more kindsof such stabilizers may be used in combination. When two or more kindsof such stabilizers are used in combination, the combination is notparticularly limited, and the mixture of a hindered amine based compoundhaving a triazine skeleton and a hindered amine based compound free of atriazine skeleton can also be used.

Examples of the hindered amine based compound (C1) having a triazineskeleton include a hindered amine compound having a triazine skeleton inany one of its molecules such as1,5,8,12-tetrakis[4,6-bis{N-(2,2,6,6-tetramethyl-4-pyperidyl)butylamino}-1,3,5-triazine-2-yl]-1,5,8,12-tetraazadodecane,N,N′,N″,N′″-tetrakis[4,6-bis{butyl-(N-methyl-2,2,6,6-tetramethylpyperidine-4-yl)amino}-triazine-2-yl]-4,7-diazadecane-1,10-diamine,poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-pyperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-pyperidyl)imino}],N,N′-bis(3-aminopropyl)ethylenediamine/2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-pyperidyl)amino]-6-chloro-1,3,5-triazinecondensate, a linear or cyclic condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-pyperidyl)hexamethylenediamine and4-tertiary octylamino-2,6-dichloro-1,3,5-triazine, a linear or cycliccondensate ofN,N′-bis(2,2,6,6-tetramethyl-4-pyperidyl)-hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, a condensate of2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpyperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, a condensate of2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpyperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, a condensate product ofN,N′-bis-(2,2,6,6-tetramethyl-4-pyperidyl)hexamethylenediamine and4-chlorohexylamino-2,6-dichloro-1,3,5-triazine, a condensation productof 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and4-butylamino-2,2,6,6-tetramethylpyperidine (CAS registered No.[136504-96-6]), and a polycondensation product ofdibutylamine/1,3,5-triazine/N,N′-bis-(2,2,6,6-tetramethyl-4-pyperidyl)-1,6-hexamethylenediamine/N-(2,2,6,6-tetramethyl-4-pyperidyl)butylamine.Those hindered amine compounds having a triazine skeleton in themolecule may be used alone, or two or more thereof may be used incombination.

Examples of the hindered amine based compound free of a triazineskeleton (C2) include hindered amine compounds such as2,2,6,6-tetramethyl-4-pyperidylstearate,1,2,2,6,6-pentamethyl-4-pyperidylstearate,2,2,6,6-tetramethyl-4-pyperidylbenzoate,N-(2,2,6,6-tetramethyl-4-pyperidyl)dodecyl succinimide,1-[(3,5-ditertiarybutyl-4-hydroxyphenyl)propionyloxyethyl]-2,2,6,6-tetramethyl-4-pyperidinyl-(3,5-ditertiarybutyl-4-hydroxyphenyl)propionate,bis(2,2,6,6-tetramethyl-4-pyperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-pyperidyl)sebacate, methyl1,2,2,6,6-pentamethyl-4-pyperidylsebacate,bis(1,2,2,6,6-pentamethyl-4-pyperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, a mixture of bis(1,2,2,6,6-pentamethyl-4-pyperidyl)sebacateand methyl-1,2,2,6,6-pentamethyl-4-pyperidylsebacate,N,N′-bis(2,2,6,6-tetramethyl-4-pyperidyl)hexamethylenediamine,tetra(2,2,6,6-tetramethyl-4-pyperidyl)butanetetracarboxylate,tetra(1,2,2,6,6-pentamethyl-4-pyperidyl)butanetetracarboxylate,bis(2,2,6,6-tetramethyl-4-pyperidyl)•di(tridecyl)butanetetracarboxylate,bis(1,2,2,6,6-pentamethyl-4-pyperidyl)•di(tridecyl)butanetetracarboxylate,3,9-bis[1,1-dimethyl-2-{tris(2,2,6,6-tetramethyl-4-pyperidyloxycarbonyloxy)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-pyperidinol/diemthylsuccinatecondensate,N,N′-bis(2,2,6,6-tetramethyl-4-pyperidyl)hexamethylenediamine/dibromoethanecondensate, bis(2,2,6,6-tetramethyl-4-pyperidyl)succinate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-pyperidyl)sebacate, a condensate ofbis(1,2,2,6,6-pentamethyl-4-pyperidyl)n-butyl-3,5-di-tertiarybutyl-4-hydroxybenzylmalonate,1-(2-hdryoxyethyl)-2,2,6,6-tetramethyl-4-hydroxypyperidine, and succinicacid, tris(2,2,6,6-tetramethyl-4-pyperidyl)nitrilotriacetate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpyperadinone),4-benzoyl-2,2,6,6-tetramethylpyperidine,4-benzoyloxy-2,2,6,6-tetramethylpyperidine,4-stearyloxy-2,2,6,6-tetramethylpyperidine,bis(1,2,2,6,6-pentamethylpyperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tertiarybutyl-benzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpyperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpyperidyl)succinate,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-pyperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-pyperidyl)-pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy-2,2,6,6-tetramethylpyperidine and4-stearyloxy-2,2,6,6-tetramethylpyperidine,N-(1,2,2,6,6-pentamethyl-4-pyperidyl)-n-dodecylsuccimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]decaneand epichlorohydroline,1,1-bis(1,2,2,6,6-pentamethyl-4-pyperidyloxycarbonyl)-2-(4-methoxyphenyl)ethane,N,N′-bisformyl-N,N′-bis(2,2,6,6-tetramethyl-4-pyperidyl)-hexamethylenediamine;a diester of 4-methoxymethylene malonic acid and1,2,2,6,6-pentamethyl-4-hydroxypyperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-pyperidyl)]siloxane; areaction product of maleic anhydride-α-olefine copolymer and2,2,6,6-tetramethyl-4-aminopyperidine or1,2,2,6,6-pentamethyl-4-aminopyperidine, [a reaction product (70%) ofdecane diacid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-pyperidyl)ester,1,1-dimethylethylhydroperoxide, and octane]-polypropylene (30%), and1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpyperidine.One kind of those hindered amine based compounds each of which is freeof a triazine skeleton may be used alone, or two or more kinds of themmay be used in combination.

A ratio at which the above component (C) is blended is not particularlylimited; the component is blended in an amount of preferably 0.1 to 50parts by mass, or particularly preferably 1.0 to 10 parts by mass withrespect to 100 parts by mass of the component (A).

In the first aspect of the curable composition of the present invention,the curable composition suitably further contains (D) a compound thatreacts with water to produce an amine compound because the anti-stainingproperty of the composition can be significantly improved. Specificsuitable examples of the above component (D) include ketimine compounds,enamine compounds, and/or aldimine compounds of amine compounds in termsof, for example, the easy availability of a raw material, storagestability, and reactivity with water.

Each of the above ketimine, enamine, and aldimine compounds can beobtained by a dehydration reaction between (D1) an amine compound and(D2) a carbonyl compound. A method of producing the above component (D)is not particularly limited, and a known method can be employed.

Examples of the above amine compound (D1) include, but not particularlylimited to, a primary amine and/or a secondary amine, and an aminecompound having at least one alkoxysilyl group in any one of itsmolecules. In particular, the amine compound having at least onealkoxysilyl group in any one of its molecules is preferable because ofits particularly excellent adhesiveness.

Examples of the primary amine include: monoamines such as butylamine,hexylamine, heptylamine, 2-ethylhexylamine, octylamine,3-methoxypropylamine, tetradecylamine, pentadecylamine, cetylamine,stearylamine, trimethylcyclohexylamine, benzylamine, and aniline;diamines such as ethylenediamine, 1,3-diaminopropane,1,2-diaminopropane, 1,4-diaminobutane, hexamethylenediamine,1,7-diaminoheptane, trimethylhexamethylene diamine, 1,8-diaminooctane,1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane,1,12-diaminododecane, 1,13-dimionotridecane, 1,14-diaminotetradecane,1,15-diminopentadecane, 1,16-diaminohexadecane, 1,17-diminoheptadecane,1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane,1,2,1-diaminoheneicosane, 1,22-diaminodocosane, 1,23-diaminotricosane,1,24-diaminotetracosane, isophoronediamine, diaminodicyclohexylmethane,3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane,xylenediamine, phenylenediamine, diaminodiphenylmethane,diaminodiethylphenylmethane, polyoxyethylenediamine, andpolyoxypropylenediamine; and polyamines such as tri(methylamino)hexane.Examples of the secondary amine include: monoamines such asdilaurylamine, distearylamine, and methyllaurylamine; and diamines suchas N,N′-dilaurylpropylamine, N,N′-distearylbutylamine,N-butyl-N′-laurylethylamine, N-butyl-N′-laurylpropylamine, andN-lauryl-N′-stearylbutylamine. Examples of the mixture of primary andsecondary amine include N-laurylpropylenediamine andN-stearylpropylenediamine. Examples of the mixture of primary andsecondary polyamine include diethylenetriamine, triethylenetetramine,and methylaminopropylamine.

Examples of the above amine compound having at least one alkoxysilylgroup in any one of its molecules include compounds each represented bythe following general formula (9):

[where n=0, 1, or 2, R¹⁶ and R¹⁷ may be identical to or different fromeach other, and each represent a hydrocarbon group having 1 to 4 carbonatoms, R¹⁸ represents a hydrocarbon group having 1 to 10 carbon atoms,and Y represents a hydrogen atom or an aminoalkyl group having 1 to 4carbon atoms.]

Here, examples of the group represented by each of R¹⁶ and R¹⁷ include:alkyl groups such as methyl, ethyl, propyl, and butyl groups; andalkenyl groups such as vinyl, allyl, propenyl, and butenyl groups. Inparticular, an alkyl group is preferable. Examples of the grouprepresented by R¹⁸ include: alkylene groups such as methylene, ethylene,propylene, and butylene; arylene groups such as a phenylene group; andalkylenearylene groups. In particular, an alkylene group is preferable.n preferably represents 0 or 1.

Specific examples of the amine compound include: compounds representedby the following formulae (10) to (17); and aminosilanes typified byN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane andN-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane. Of those,γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropylmethyldimethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, or the like isparticularly preferable because in addition improved adhesiveness can beobtained.

The carbonyl compound (D2) includes known compounds, and examplesthereof include, but not limited to: aldehydes such as acetaldehyde,propionealdehyde, n-butylaldehyde, isobutylaldehyde, n-amylaldehyde,isohexylaldehyde, diethylacetaldehyde, glyoxal, benzaldehyde, andphenylacetaldehyde; cyclic ketones such as cyclopentanone,trimethylcyclopentanone, cyclohexanone, methylcyclohexanone, andtrimethylcyclohexanone; aliphatic ketones such as acetone,methylethylketone, methylpropylketone, methylisopropylketone,methylisobutylketone, methyl-tert-butylketone, diethylketone,dipropylketone, diisopropylketone, dibutylketone, and diisobutylketone;aromatic ketones such as acetophenone, benzophenone, and propiophenone;and β-dicarbonyl compound represented by the following general formula(18), such as acetylacetone, methyl acetoacetate, ethyl acetoacetate,dimethylmalonate, diethylmalonate, methylethylmalonate, anddibenzoylmethane.

Of those, methyl isobutyl ketone, dipropyl ketone, phenylacetaldehyde,and a β-dicarbonyl compound having an active methylene group [compoundrepresented by the following general formula (18)] are more preferable:

[Chemical Formula 11]

R¹⁹—CO—CH₂—CO—R²⁰  (18)

[where R¹⁹ and R²⁰ may be identical to or different from each other, andeach represent an alkyl group having 1 to 16 carbon atoms (such as amethyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl,undecyl, or hexadecyl group), an aryl group having 6 to 12 carbon atoms(such as a phenyl, tolyl, hexyl, or naphthyl group), or an alkoxyl grouphaving 1 to 4 carbon atoms (such as a methoxy, ethoxy, propoxy, orbutoxy group).]

The above compound that reacts with water to produce an amine compoundhaving at least one alkoxysilyl group in any one of its molecules in thecomponent (D) of the present invention is not particularly limited, anda compound obtained by a known production method can be used; a compoundhaving a monomer purity of 50 to 95%, preferably 70 to 95%, or morepreferably 80 to 95%, and an amino group sealing rate of 90% or more, orpreferably 95% or more is suitably used.

A ratio at which the above component (D) is blended is not particularlylimited; the component (D) is blended in an amount of preferably 0.05 to50 parts by mass, or particularly preferably 1.0 to 20 parts by masswith respect to 100 parts by mass of the component (A). One kind of theabove the compound that reacts with water to produce an amine compoundmay be used alone, or two or more kinds of such compounds may be used incombination.

In addition, in the first aspect of the curable composition of thepresent invention, the curable composition suitably further contains(D1) an amine compound and (D2) a carbonyl compound in order that theanti-staining property of the composition may be improved. The aminecompound and the carbonyl compound exemplified in the description of thecomponent (D) can be similarly used as the components (D1) and (D2),respectively. The above components (D1) and (D2) cause a dehydrationreaction in the blend of the components. The dehydration reaction, whichmay be performed while a treatment such as a heat treatment is performedas required, can be advanced with the passage of time without theperformance of any particular step.

A ratio at which each of the components (D1) and (D2) is blended is notparticularly limited; each of the components (D1) and (D2) is blended inan amount of preferably 0.05 to 50 parts by mass, or particularlypreferably 0.1 to 20 parts by mass with respect to 100 parts by mass ofthe component (A). Further, a ratio “[molar amount of component(D1)]/[molar amount of component (D2)]” is in the range of preferably0.1 to 5.0, or more preferably 0.5 to 2.0. One kind of the amine orcarbonyl compound may be used alone, or two or more kinds of such amineor carbonyl compounds may be used in combination.

In the first aspect of the curable composition of the present invention,the curable composition may be blended with any one of: substances suchas an adhesion imparting agent, a physical property adjuster, a filler,a curing catalyst, a plasticizer, a thixotropic agent, a dehydratingagent (storage stability improver), a tackifier, a sagging inhibitor, anantioxidant, a flame retardant, a colorant, and a radical polymerizationinitiator; and various solvents such as toluene and an alcohol inaddition to the above-mentioned components as required, or may beblended with any other polymer compatible with the curable composition.In addition, an ultraviolet ray absorbing agent except the component(B), that is, the triazine based ultraviolet ray absorbing agent such asa benzotriazole based, triazine based, benzophenone based, benzoatebased, or salicylic acid based ultraviolet ray absorbing agent or alight stabilizer except the component (C), that is, the hindered aminebased light stabilizer may be further added to the curable compositionof the present invention.

The above other polymer compatible with the curable composition isparticularly preferably any one of various polyethers, especially, forexample, a polyether having a silicon functional group.

Examples of the adhesion imparting agent include various silane couplingagents such as: aminosilanes includingaminoethylaminopropyltrimethoxysilane,aminoethylaminopropylmethyldimethoxysilane,aminoethylaminopropylmethylmethoxysilane; epoxy silanes includingγ-glycidoxypropyltrimethoxysilane; acrylsilanes includingγ-methacryloxypropyltrimethoxy silane; mercaptosilanes includingγ-mercaptopropyltrimethoxy silane; and isocyanate silanes includingγ-isocyanate propyltrimethoxysilane. Those adhesion imparting agents maybe used alone, or two or more thereof may be used in combination.

The above physical property adjuster is added for the purpose ofimproving the tensile property of the curable composition. Examples ofthe above physical property adjuster include silicon compounds eachhaving one silanol group in any one of its molecules, such astriphenylsilanol, trialkylsilanol, dialkylphenylsilanol, anddiphenylalkylsilanol. The examples further include various silanecoupling agents such as silicon compounds each of which hydrolyzes toproduce a compound having one silanol group in any one of its moleculesincluding triphenylmethoxysilane, trialkylmethoxysilane,dialkylphenylmethoxysilane, diphenylalkylmethoxysilane,triphenylethoxysilane, and trialkylethoxysilane. One kind of the abovephysical property adjusters may be used alone, or two or more kinds ofthem may be used in combination.

The above filler is added for the purpose of reinforcing a cured productmade of the curable composition. Examples of the above filler includecalcium carbonate, magnesium carbonate, diatomaceous earth hydratesilicic acid, hydrate silicic acid, silicic acid anhydride, calciumsilicate, silica, titanium dioxide, clay, talc, carbon black, slatepowder, mica, kaolin, and zeolite. Of those, calcium carbonate ispreferable, and calcium carbonate treated with an aliphatic acid is morepreferable. In addition, a glass bead, a silica bead, an alumina bead, acarbon bead, a styrene bead, a phenol bead, an acrylic bead, poroussilica, a Shirasu balloon, a glass balloon, a silica balloon, a saranballoon, an acrylic balloon, or the like can also be used. Of those, theacrylic balloon is more preferable because a reduction in elongation ofthe composition after the curing of the composition is small. One kindof the above fillers may be used alone, or two or more kinds of them maybe used in combination.

The above plasticizer is added for the purposes of: improving theelongation property of the composition after the curing of thecomposition; and enabling a reduction in modulus of a cured product.Examples of the plasticizer include: phosphates such as tributylphosphate and tricresyl phosphate; phthalates such as dioctyl phthalate(DOP), dibutyl phthalate, and butyl benzyl phthalate; aliphaticmonobasic acid esters such as glycerin monooleate; aliphatic dibasicacid esters such as dibutyl adipate and dioctyl adipate; glycol esterssuch as polypropylene glycol; aliphatic esters; epoxy plasticizers;polyester based plasticizers; polyethers; and polystyrenes. One kind ofthe above plasticizers may be used alone, or two or more kinds of themmay be used in combination.

Examples of the above thixotropic agent include: an inorganicthixotropic agent such as colloidal silica or asbestos powder; anorganic thixotropic agent such as organic bentonite, modified polyesterpolyol, or an aliphatic amide; a hydrogenated castor oil derivative; analiphatic amide wax; aluminum stearate; and barium stearate. One kind ofthe above thixotropic agents may be used alone, or two or more kinds ofthem may be used in combination.

The above dehydrating agent is added for the purpose of removingmoisture during the storage of the composition. Examples of thedehydrating agent include silane compounds such asvinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane,methyltrimethoxysilane, and methyltriethoxysilane.

The above antioxidant is used for preventing the oxidation of a curedsealing material to improve the weather resistance of the material, andis, for example, a hindered phenol based antioxidant. Examples of thehindered phenol based antioxidant include, but not limited to,pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],thiodiethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],octadecyl[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],N,N′-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropioamide],benzene propionic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy C7-C9 sidechain alkylester, 2,4-dimethyl-6-(1-methylpentadecyl)phenol,diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate,3,3′,3″,5,5′,5″-hexane-tert-butyl-4-a,a′,a″-(mesitylene-2,4,6-tolyl)tri-p-cresol,calciumdiethylbis[[[3,5-bis-(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate],4,6-bis(octylthiomethyl)-o-cresol,ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate],hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione,a reaction product of N-phenylbenzeneamine and 2,4,4-trimethylpentene,and2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol.One kind of the above antioxidants may be used alone, or two or morekinds of them may be used in combination.

The second aspect of the curable composition of the present inventioncontains the following components (E), (F), (G), and (H) as essentialcomponents:

(E) an organic polymer containing a crosslinkable silyl group;

(F) a (meth)acrylic polymer containing an epoxy group;

(G) a divalent tin organic carboxylate; and

(H) an organic amine compound.

The organic polymer containing a crosslinkable silyl group exemplifiedin the description of the component (A) according to the first aspect ofthe curable composition of the present invention can be similarly usedas (E) the organic polymer containing a crosslinkable silyl group.

(F) The (meth)acrylic polymer containing an epoxy group has a weightaverage molecular weight of preferably 1,000 to 7,500, more preferably1,500 to 6,000, or still more preferably 2,000 to 5,500. A weightaverage molecular weight in excess of 7,500 is not preferable because asufficient plasticizing effect is not exerted, and workabilitydeteriorates. A weight average molecular weight of less than 1,000 isnot preferable too because a low-molecular-weight polymer bleeds, andhence the anti-staining property of the composition is reduced. Thenumber of epoxy groups in the polymer (F), which is not particularlylimited, is preferably 0.05 or more, or more preferably 0.1 or more onaverage in one molecule of the polymer. The (meth)acrylic polymercontaining an epoxy group functions as a plasticizer and an aminecatcher. An epoxy group has polarity, and an increase in polarity of thepolymer improves the affinity of the polymer for top coating paint, soadhesiveness between the polymer and the top coating paint may improve.

Although a method of producing (F) the (meth)acrylic polymer containingan epoxy group is not particularly limited, the polymer can bespecifically obtained by copolymerizing a (meth)acrylic monomercontaining an epoxy group (such as glycidyl (meth)acrylate) or bycausing an epoxy group-containing compound to react with a (meth)acrylicpolymer containing a functional group. The latter method involvingcausing an epoxy group-containing compound to react with a (meth)acrylicpolymer containing a functional group is, for example, a methodinvolving causing glycidol to react with a polymer having an isocyanategroup.

The (meth)acrylic polymer can be produced, but not particularly limitedto, by (co)polymerizing one or more kinds of (meth)acrylic monomers suchas (meth)acrylic acid, (meth)acrylate, (meth)acrylonitrile, and(meth)acrylamide with a known method. As the (meth)acrylic monomer,(meth)acrylate is particularly preferred.

Examples of the (meth)acrylate include: alkyl (meth)acrylates such asmethyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate,isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate,s-butyl (meth)acrylate, t-butyl (meth)acrylate, neopentyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate,lauryl (meth)acrylate, tridecyl (meth)acrylate, and stearyl(meth)acrylate; aliphathic alkyl (meth)acrylates such as cyclohexyl(meth)acrylate, isobornyl (meth)acrylate, and tricyclodecynyl(meth)acrylate; and hetero atom-containing (meth)acrylates such as2-methoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate,chloroethyl (meth)acrylate, and trifluoroethyl (meth)acrylate, andtetrahydroflufuryl (meth)acrylate. Of those, methyl methacrylate, ethylacrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,methoxyethyl acrylate, and cyclohexyl acrylate are preferred in regardto obtaining the balance of plasticity. In addition to those(meth)acrylates, any other copolymerizable monomer may be used to suchan extent that the physical properties of the composition are notimpaired. Examples of such monomer include: α-olefins such as ethylene,propylene, and isobutylene; chloroethylenes such as vinyl chloride andvinylidene chloride; and alkyl vinyl ethers such as ethyl vinyl etherand butyl vinyl ether.

A ratio at which the component (F) is blended is not particularlylimited; the component is used in an amount of preferably 5 to 150 partsby mass, more preferably 10 to 120 parts by mass, or still morepreferably 15 to 100 parts by mass with respect to 100 parts by mass ofthe component (E). When the amount is less than 5 parts by mass, asufficient plasticizing effect or sufficient restoring property cannotbe obtained. When the amount exceeds 150 parts by mass, the componentbleeds on the surface of the composition, so the anti-staining propertyof the composition deteriorates in some cases. Only one kind of the(meth)acrylic polymer containing an epoxy group may be used, or two ormore kinds of such polymers may be used in combination.

Examples of (G) the divalent tin organic carboxylate include tin(II)octylate, tin(II) naphthenate, and tin(II) stearate. A ratio at whichthe component (G) is blended is not particularly limited; the componentis blended in an amount of preferably 0.001 to 10 parts by mass withrespect to 100 parts by mass of the component (E). Only one kind of thedivalent tin organic carboxylate may be used, or two or more kinds ofsuch salts may be used as a mixture.

Examples of the organic amine compound (H) include diethylenetriamine,triethyelenetetramine, tetraethylenepentamine, butylamine, hexylamine,octylamine, decylamine, laurylamine, hexamethylenediamine,triethanolamine, dibutylamine, diethanolamine,N,N,N′,N′-tetramethyl-1,3-butanediamine, benzylamine, cyclohexylamine,dodecamethylenediamine, diemethylethylenediamine, dim ethylaminoethanol,N,N,N′,N′-tetramethylethylenediamine, triethylamine,N,N-dimethylaniline, and diemethylbenzylaniline. In addition, a compoundthat reacts with water to produce an organic amine such as ketimine canalso be used as the organic amine compound.

A ratio at which the above component (H) is blended is not particularlylimited; the component is blended in an amount of preferably about 0.001to 10 parts by mass with respect to 100 parts by mass of the component(E). One kind of the above organic amine compound may be used alone, ortwo or more kinds of such compounds may be used in combination.

In the second aspect of the curable composition of the presentinvention, the curable composition may be blended with any one of:various other additives such as a curing catalyst, an adhesion impartingagent, a physical property adjuster, a filler, a plasticizer, athixotropic agent, a dehydrating agent (storage stability improver), atackifier, a sagging inhibitor, an ultraviolet ray absorbing agent, anantioxidant, a flame retardant, a colorant, and a radical polymerizationinitiator; and various solvents such as toluene and an alcohol inaddition to the above-mentioned components as required.

The third aspect of the curable composition of the present inventioncontains the following components (I), (J), and (K) as essentialcomponents:

(I) a reactive organic polymer containing at least one crosslinkablesilyl group in any one of its molecules;

(J) a reactive organic polymer containing less than one crosslinkablesilyl group in any one of its molecules; and

(K) thermally expandable hollow spheres as essential components.

The above thermally expandable hollow spheres are microcapsules eachmade of a thermoplastic resin and each including a volatile expansiveadditive that is brought into a gas state at a temperature equal to orlower than the softening point of the resin. In other words, thethermally expandable hollow spheres are the following substances: avolatile substance in each of the substances expands by virtue ofheating, and, at the same time, a resin composition as the outer shellof each of the substances softens, whereby the volume of each of thesubstances expands to be many times as large as that in an initialstate. A hydrocarbon based liquid having a low boiling point has beenconventionally used as the volatile expansive additive, and it has notbeen acknowledged that the thermally expandable hollow spheres are eacha substance having high combustibility and imparting flame resistance.The inventors of the present invention have found that a curablecomposition having excellent fire resistance while maintaining goodphysical properties and safety can be obtained at a low cost byincorporating the thermally expandable hollow spheres (K) in an amountof 0.01 part by mass or more to less than 20 parts by mass, preferably0.01 part by mass or more to less than 15 parts by mass, or morepreferably 0.03 part by mass or more to 10 parts by mass or less withrespect to a total of 100 parts by mass of the reactive organic polymercontaining at least one crosslinkable silyl group in any one of itsmolecules (I) and the reactive organic polymer containing less than onecrosslinkable silyl group in any one of its molecules (J). An additionalamount of the thermally expandable hollow spheres (K) of 20 parts bymass or more is not desirable because the physical properties of thecurable composition are reduced, and a foaming heat insulating layer tobe formed when the composition is exposed to flame becomes so huge thatthe fire resistance of the composition is reduced.

In the curable composition of the present invention, the hardness of arubber-like elastic body after the curing of the composition (rubberhardness meter: JIS A type) is preferably 40 or less, or more preferably35 or less.

Hereinafter, the reactive organic polymer containing at least onecrosslinkable silyl group in any one of its molecules (I) to be used inthe present invention will be described. A reactive organic polymercontaining at least one crosslinkable silyl group in any one of itsmolecules is used as the polymer (I). An organic polymer containing atleast one crosslinkable silyl group in any one of its molecules out ofthe organic polymers each containing a crosslinkable silyl groupexemplified in the description of the component (A) according to thefirst aspect of the curable composition of the present invention can besimilarly used as the organic polymer containing a crosslinkable silylgroup (I).

Next, the reactive organic polymer containing less than onecrosslinkable silyl group in any one of its molecules (J) to be used inthe present invention will be described. An organic polymer containingzero or more and less than one crosslinkable silyl group in any one ofits molecules is used as the polymer (J). The crosslinkable silyl groupis preferably one represented by the general formula (1). Specificsuitable examples of the polymer include a polyoxyalkylene basedpolymer, a vinyl-modified polyoxyalkylene based polymer, a vinyl basedpolymer, a polyester polymer, and a (meth)acrylate polymer each of whichcontains zero or more and less than one crosslinkable silyl group onaverage in any one of its molecules and the main chain of each of whichmay contain organosiloxane, and a copolymer or mixture of two or more ofthem. In particular, in terms of physical properties such as tensilestrength and a modulus after the curing of the composition, apolyoxyalkylene based polymer, a (meth) acrylic polymer, and a(meth)acrylic-modified polyoxypropylene polymer each of which containsless than one, or preferably less than 0.7 crosslinkable silyl group onaverage in any one of its molecules and the main chain of each of whichmay contain organosiloxane, and a copolymer or mixture of two or more ofthem are preferable, and such (meth)acrylic polymer is more preferable.

A method of producing the polymer (J) is not particularly limited, andthe polymer can be produced by, for example, setting the number ofcrosslinkable silyl groups present in one molecule of an organic polymercontaining a crosslinkable silyl group to less than one in the method ofproducing the organic polymer described in the description of thepolymer (A). A method of producing the polymer (J) is specifically, forexample, a production method employed in Synthesis Example 4 to bedescribed later.

In the present invention, the above reactive organic polymer (J)desirably has a weight average molecular weight of 2,000 or more to50,000 or less, or preferably 2,000 or more to 30,000 or less and anarrow molecular weight distribution because the viscosity of thepolymer before the curing of the composition is so low that the polymercan be easily handled, and the physical properties of the compositionafter the curing of the composition such as strength, an elongationrate, and a modulus are suitable. Only one kind of the above polymer (J)may be used, or two or more kinds of such polymers may be used incombination.

A ratio at which the polymer (J) is blended is not particularly limited;the polymer (J) is used in an amount of preferably 10 to 300 parts bymass, or more preferably 20 to 200 parts by mass with respect to 100parts by mass of the polymer (I).

Hereinafter, the thermally expandable hollow spheres (K) to be used inthe present invention will be described. Examples of the thermallyexpandable hollow spheres (K) include those disclosed in JP 42-26524B,JP49-14381B, JP63-122713A, JP63-122745A, JP4-08534A, JP56-113338A,JP11-209504A, JP 2000-191817A, JP 2002-12693A, JP 2002-363537A, and U.S.Pat. No. 4,722,943. To be specific, spheres each containing a foamingagent in a shell part composed of, for example, polyvinylidene chloride,a copolymer of vinylidene chloride and acrylonitrile, polyacrylonitrile,or a copolymer of acrylonitrile and methyl acrylate and each having aparticle diameter of about 1 to 50 μm like a “Microsphere” manufacturedby Matsumoto Yushi-Seiyaku Co., Ltd are used. Examples of the foamingagent include: low-boiling-point hydrocarbons such as ethane, propane,butane, pentane, hexane, heptane, and cyclopentane; halogenatedhydrocarbons such as methyl chloride and ethyl chloride; HCFCs such as1,1-dichloro-1-fluoroethane; and HFCs such as 1,1,1,2-tetrafluoroethane.Only one kind of the above hollow spheres (K) may be used, or two ormore kinds of the spheres may be used in combination.

In addition, any other foaming agent may be added to the compositionaccording to the third aspect of the curable composition of the presentinvention. The kind of the foaming agent is not particularly limited,and an ordinary agent can be used. In addition, multiple agents may becombined. Ammonium polyphosphate is particularly desirably used as theother foaming agent; the generation of an ammonia gas caused by thehydrolysis of ammonium polyphosphate and phosphorus in ammoniumpolyphosphate promote the carbonization of any other substance to causethe substance to produce an incombustible carbonized layer, wherebyammonium polyphosphate has an action of improving the fire resistance ofthe composition. In addition, ammonium polyphosphate described above haspoor water resistance, so coated ammonium polyphosphate with improvedwater resistance is more desirable.

In addition, in the third aspect of the curable composition of thepresent invention, any one of: various additives such as a flameretardant, a plasticizer, a filler, a curing catalyst, an adhesionimparting agent, a physical property adjuster, a thixotropic agent, adehydrating agent (storage stability improver), a tackifier, a sagginginhibitor, an ultraviolet ray absorbing agent, an antioxidant, a flameretardant, a colorant, and a radical polymerization initiator; andvarious solvents such as toluene and an alcohol may be added to thecurable composition as required. Those additives are not particularlylimited, and an ordinary additive can be used. In addition, multipleadditives may be combined.

The curable composition of the present invention can be turned into aone-component liquid or a two-component liquid as required. The curablecomposition of the present invention, which is most suitably used in asealing material, can be used in, for example, an adhesive, apressure-sensitive adhesive, a coating material, or a potting materialas required. The curable composition of the present invention can beused for, for example, various structures, automobiles, civilengineering, and electrical and electronic fields.

A fire-resistant structure capable of passing a fire resistance testdescribed in JIS A 1304 can be formed with ease at a low cost by thecombined use of a sealing material having fire resistance and using thethird aspect of the curable composition of the present invention as anavailable ingredient and a wall material having fire resistance.

The formation method of the present invention involves forming afire-resistant structure by using a wall material having fire resistanceand the sealing material having fire resistance of the presentinvention. FIG. 1 is a perspective view showing an example of afire-resistant structure to be formed by the formation method of thepresent invention. FIG. 2 is a top view of FIG. 1. In FIGS. 1 and 2, awall material 10 having fire resistance and a wall material 11 havingfire resistance are brought into abutment with each other through afiller 14 such as a back-up material or a bond breaker provided for anabutting portion A, and the abutting portion A is filled with a sealingmaterial 12 of the present invention, whereby a fire-resistant structure13 is formed.

Examples of the above wall material 10 having fire resistance includeprecast concrete (PC), an autoclaved lightweight aerated concrete panel(ALC), and a ceramic covering material for a fire-resistant structure.The above filler 14 such as a back-up material or a bond breaker is notparticularly limited, and a wide variety of known fillers can be used; afire-resistant filler such as the “Litoflex” manufactured by NICHIASCorporation is more preferably used because the fire resistance of thefire-resistant structure is additionally improved.

The fire-resistant structure to be obtained by the present invention canform a foaming heat insulating layer when exposed to flame to shield,for example, heat, flame, smoke, and a gas generated by combustion. Inaddition, according to the present invention, there can be provided astructure having extremely excellent fire resistance not only when aspecial back-up material having fire resistance is used but also when anordinary back-up material (such as a product extruded or cut out frompolyethylene) is used.

EXAMPLES

Hereinafter, the present invention will be described more specificallyby way of examples. Needless to say, however, these examples areexemplary, and should not be construed as being limitative.

Examples 1 to 12 and Comparative Examples 1 to 4 Synthesis Example 1Synthesis of Ketimine Compound

500 g of a primary amine dissolved by heating (stearylamine; trade name“FIRMIN 80” manufactured by KAO CORPORATION, amine value 207) wereloaded into a stirring vessel provided with a heating device and anester tube. After that, 203 g of a carbonyl compound (methyl isobutylketone, molecular weight: 100.2) were added to the vessel while theamine was stirred. 130 g of toluene were further added to the mixture.Then, the resultant was heated to 110 to 150° C., continuously stirredfor 3 hours, and dehydrated from the ester tube. Next, excessive amountsof the carbonyl compound and toluene were removed under reducedpressure, whereby a ketimine compound was obtained.

Synthesis Example 2 Synthesis of Acrylic Polymer 1 ContainingCrosslinkable Silyl Group

The temperature of a pressure stirring tank type reactor provided withan electrothermal heater and having a volume of 1,000 ml was kept at200° C. Next, while the pressure in the reactor was kept constant, amonomer mixture composed of 84 parts of butyl acrylate as an acrylatemonomer, 16 parts of γ-methacryloxypropyltrimethoxysilane as ahydrolyzable silyl group-containing monomer, and 1 part of di-t-butylperoxide as a polymerization initiator started to be continuouslysupplied from a raw material tank to the reactor at a constant supplyspeed (80 g/min, residence time: 12 minutes), and a reaction liquidcorresponding to the supplied amount of the monomer mixture wascontinuously pulled out from the outlet of the reactor.

Immediately after the initiation of the reaction, the reactiontemperature reduced once, and then an increase in temperature due toheat of polymerization was observed. The reaction temperature was keptat 250 to 251° C. by controlling the heater. The time point when thetemperature became stable after the initiation of the supply of themonomer mixture was defined as the starting point of the collection ofthe reaction liquid. The reaction was continued for 25 minutes from thestarting point, whereby 2 kg of the monomer mixed liquid were supplied,and 1.9 kg of the reaction liquid were recovered. After that, thereaction liquid was introduced to a thin-film evaporator, and volatilecomponents such as an unreacted monomer were separated, whereby acondensed liquid was obtained. Gas chromatographic analysis confirmedthat no unreacted monomer was present in the condensed liquid. Theresultant polymer had a number average molecular weight of 2,000 interms of polystyrene measured by gel permeation chromatography usingtetrahydrofuran as a solvent and a weight average molecular weight of4,800 in terms of polystyrene similarly measured. In addition, thenumber of crosslinkable silyl groups per one molecule of the polymer was1.29. An acrylic polymer 1 having 1.29 crosslinkable silyl groups onaverage in any one of its molecules was obtained.

Example 1

As shown in Table 1, predetermined amounts of a modified siliconepolymer SA 100S (manufactured by Kaneka Corporation) as the component(A), that is, the organic polymer containing a crosslinkable silylgroup, a 1577 FF (manufactured by Ciba Specialty Chemicals) as thecomponent (B), that is, the triazine based ultraviolet ray absorbingagent, a CHIMASSORB 119FL (manufactured by Ciba Specialty Chemicals) asthe component (C), that is, the light stabilizer, a plasticizer, afiller, and a dehydration treatment agent were loaded, and the blendedsubstances were mixed and stirred under heat and reduced pressure at110° C. for 2 hours, whereby the blended substances were dehydrated.Further, predetermined amounts of the ketimine compound obtained inSynthesis Example 1 as the component (D), dibutyltin diacetylacetonateas a curing catalyst, and an aminosilane compound as a silane couplingagent were added to and blended in the resultant under stirring, wherebya curing composition was prepared.

TABLE 1 Example No. Component Blended substances 1 2 3 4 5 6 7 8 9 10 1112 (A) Acrylic polymer containing crosslinkable silyl 100 50 100 100 100100 100 100 100 — — — group at terminal*¹ Acrylic polymer containingcrosslinkable — — — — — — — — — 100 — — silyl group*² Acrylic-modifiedpolyoxyalkylene polymer — — — — — — — — — — 100 — containingcrosslinkable silyl group*³ Polyoxyalkylene polymer containingcrosslinkable — 50 — — — — — — — — — 100 silyl group*⁴ (B) Triazinebased ultraviolet ray absorbing agent*⁵ 1 1 1 1 1 1 1 1 1 1 1 1 (C)Hindered amine based compound 1 1 1 — — — 0.5 — — 1 1 1 containingtriazine skeleton*⁶ Hindered amine based compound — — — — 1 — — — — — —— containing triazine skeleton*⁷ Hindered amine based compound — — — — —1 — — — — — — containing triazine skeleton*⁸ Hindered amine basedcompound*⁹ — — — 1 — — 0.5 — — — — — Hindered amine based compound*¹⁰ —— — — — — — 1 1 — — — (D) Ketimine compound*¹¹ 3 3 — — — — — — — — — —Antioxidant*¹² — — — — — — — — 1 — — — Plasticizer*¹³ 60 60 60 60 60 6060 60 60 60 60 60 Filler*¹⁴ 140 140 140 140 140 140 140 140 140 140 140140 Dehydration treatment agent*¹⁵ 1 1 1 1 1 1 1 1 1 1 1 1 Silanecoupling agent*¹⁶ 2 2 2 2 2 2 2 2 2 2 2 2 Curing catalyst*¹⁷ 2 2 2 2 2 22 2 2 2 2 2 The amounts of the blended substances in Table 1 are eachrepresented by “part(s) by mass”, and the symbols *1 to *17 representthe following products: *¹an acrylic polymer containing a crosslinkablesilyl group at a terminal of any one of its molecules synthesized by aliving radical polymerization method (trade name; SA 100S, manufacturedby Kaneka Corporation); *²the acrylic polymer 1 containing acrosslinkable silyl group obtained in Synthesis Example 2; *³anacrylic-modified polyoxyalkylene polymer containing a crosslinkablesilyl group (trade name; S911, manufactured by Kaneka Corporation); *⁴apolyoxyalkylene polymer containing a crosslinkable silyl group (tradename; S203, manufactured by Kaneka Corporation); *⁵a triazine basedultraviolet ray absorbing agent (trade name; 1577 FF, manufactured byCiba Specialty Chemicals); *⁶a hindered amine based compound having atriazine skeleton (trade name; CHIMASSORB 119FL, manufactured by CibaSpecialty Chemicals); *⁷a hindered amine based compound having atriazine skeleton (trade name; CHIMASSORB 2020FL, manufactured by CibaSpecialty Chemicals); *⁸a hindered amine based compound having atriazine skeleton (trade name; CHIMASSORB 944FD, manufactured by CibaSpecialty Chemicals); *⁹a hindered amine based compound free of atriazine skeleton (containing a —NCH₃ group, trade name; LA62,manufactured by Ashahi Denka Co., Ltd); *¹⁰a hindered amine basedcompound free of a triazine skeleton (containing a —NOR group, tradename; TINUVIN 123, manufactured by Ciba Specialty Chemicals); *¹¹theketimine compound obtained in Synthesis Example 1; *¹²an antioxidant(trade name; AO-20, manufactured by Ashahi Denka Co., Ltd); *¹³anacrylic polymer (trade name; UP1000, manufactured by TOAGOSEI CO.,LTD.); *¹⁴calcium carbonate (trade name; CCR, manufactured by ShiraishiKogyo Kaisha, Ltd.); *¹⁵a moisture absorbent (trade name; KBM1003,manufactured by Shin-Etsu Chemical Co., Ltd.); *¹⁶an aminosilanecompound (trade name; KBM603, manufactured by Shin-Etsu Chemical Co.,Ltd.); and *¹⁷dibutyltin diacetylacetonate (trade name; NEOSTAN U220,manufactured by NITTO KASEI CO., LTD.).

Examples 2 to 12 and Comparative Examples 1 to 4

Curable compositions were each prepared in the same manner as in Example1 except that the blended substances and a ratio at which each of thesubstances was blended were changed as shown in each of Tables 1 and 2.

TABLE 2 Comparative Example No. Component Blended substances 1 2 3 4 (A)Acrylic polymer containing 100 — — — crosslinkable silyl group atterminal*¹ Acrylic polymer containing — 100 — — crosslinkable silylgroup*² Acrylic-modified — — 100 — polyoxyalkylene polymer containingcrosslinkable silyl group*³ Polyoxyalkylene polymer — — — 100 containingcrosslinkable silyl group*⁴ Ultraviolet ray absorbing 1 1 1 1 agent*¹⁸(C) Hindered amine based 1 1 1 1 compound*⁹ Plasticizer*¹³ 60 60 60 60Filler*¹⁴ 140 140 140 140 Dehydration treatment 1 1 1 1 agent*¹⁵ Silanecoupling agent*¹⁶ 2 2 2 2 Curing catalyst*¹⁷ 2 2 2 2 The amounts of theblended substances in Table 2 are each represented by “part(s) by mass”,the symbols *1 to 4, 9, and 13 to 17 each have the same meaning as thatof Table 1, and the symbol *18 represents the following product: *¹⁸abenzotriazole based ultraviolet ray absorbing agent (trade name; LA36,manufactured by Ashahi Denka Co., Ltd).

Each of the above resultant curable compositions was subjected to thefollowing performance tests. Tables 3 and 4 show the results.

(1) Weather Resistance Test

Each of the above curable compositions was molded into a sheet having athickness of 5 mm, and the sheet was aged at 23° C. for 7 days andsubsequently at 30° C. for 7 days, whereby the thick layer portion of acured product sheet was obtained. In addition, each of the above curablecompositions was molded into a sheet having a thickness of 0.2 mm byusing a metal spacer as a sheet having a thickness of 0.2 mm, and theresultant sheet was aged at 23° C. for 7 days and subsequently at 30° C.for 7 days, whereby the thin layer portion of the cured product sheetwas obtained. Each of the resultant thick layer portion and theresultant thin layer portion was irradiated with light from a DaiplaMetal Weather (manufactured by Daipla Wintes Co., Ltd., model KU-R4-A),and the deterioration of the surface of each of the layers with time wasvisually observed.

Evaluation Criteria of Weather Resistance Test

The thin layer portion was evaluated for time period needed completewhitening.

x: less than 200 hours, Δ: 200 hours or more and less than 500 hours, ∘:500 hours or more and less than 1,000 hours, ⊚: 1,000 hours or more.

The thick layer portion was evaluated for time period needed for thegeneration of a crack.

x: less than 500 hours, Δ: 500 hours or more and less than 800 hours, ∘:800 hours or more and less than 1,200 hours, ⊚: 1,200 hours or more.

(2) Anti-Staining Property Test

Each of the above curable compositions was molded into a sheet having athickness of 10 mm. The sheet was exposed to the outdoors in the southdirection at an angle of 45° for 6 months, and the presence or absenceof staining on the surface of the sheet was visually observed. The casewhere the staining was severe was denoted by x, the case where nearly nostaining was present was denoted by ∘, and the case where no stainingwas present was denoted by ⊚.

(3) Elongation Rate Test

An abutting test body having a joint length of 50 mm, a joint width of12 mm, and a joint depth of 12 mm was produced by using each of theresultant curable compositions and a ceramic siding material (trade name“MOEN M” manufactured by NICHIHA CORPORATION). It should be noted thatthe body was aged under standard conditions of 23° C. and 50% RH for 14days. The produced test body was subjected to a tensile strength test ata tension speed of 50 mm/min, and its maximum elongation rate wasmeasured.

TABLE 3 Example No. 1 2 3 4 5 6 7 8 9 10 11 12 Weather Thin ⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ◯ ◯ resistance layer portion Thick ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ layerportion Anti-staining ⊚ ⊚ X X X X X X X X X X property Elongation rate450 650 400 400 400 400 400 400 400 150 500 600 [%]

TABLE 4 Comparative Example No. 1 2 3 4 Weather Thin layer portion Δ Δ XX resistance Thick layer portion ◯ ◯ Δ X Anti-staining property X X X XElongation rate [%] 400 150 500 600

As shown in Tables 3 and 4, each of the curable compositions of Examples1 to 12 showed excellent weather resistance in not only a thick layerportion but also a thin layer portion. In addition, each of the curablecompositions of Examples 1 and 2 to each of which the ketimine compoundhad been added showed significantly improved anti-staining property.Further, each of the curable compositions of Examples 1 to 9 each usinga (meth)acrylic polymer having a crosslinkable silyl group at a terminalof any one of its molecules as the component (A) showed extremely goodweather resistance and a high elongation rate particularly useful in asealing material.

Examples 13 to 17 and Comparative Examples 5 to 8 Synthesis Example 3Synthesis of Acrylic Polymer Containing Crosslinkable Silyl Group

85 parts by weight of n-butyl acrylate, 15 parts by weight of methylmethacrylate, 10 parts by weight ofγ-methacryloxypropyltrimethoxysilane, and 0.1 part by weight oftitanocene dichloride as a metal catalyst were loaded into a flaskprovided with a stirring device, a nitrogen gas-introducing tube, atemperature gauge, and a reflux condenser, and the contents in the flaskwere heated to 70° C. while a nitrogen gas was introduced into theflask.

Next, 1.5 parts by weight of 3-mercaptopropyltrimethoxysilane were addedin one stroke to the flask the inside of which had been sufficientlyreplaced with a nitrogen gas while the contents in the flask werestirred. After the addition of 1.5 parts by weight of3-mercaptopropyltrimethoxysilane, heating and cooling were performed for4 hours in order that the temperature of the contents in the flaskduring the stirring might be kept at 70° C. Further, heating wasperformed in order that the temperature of the contents in the flaskduring the stirring might be kept at 90° C., and a polymerizationreaction was continued for 2 hours. After that, 0.1 part by weight ofazobisisobutyronitrile as a radical polymerization initiator was addedto the flask, and the polymerization was continued for an additional 1hour, whereby the amount of a remaining monomer was reduced.

After the above-mentioned reaction for a total of 7 hours, thetemperature of the reaction product was returned to room temperature,and the polymerization was terminated. An acrylic polymer containing acrosslinkable silyl group, the polymer having a rate of polymerizationof 98.7%, Mw of 34,000, Mn of 18,000, a dispersion index of 1.9, and asilylation rate of 1.1, was obtained.

Example 13

As shown in Table 5, predetermined amounts of a modified siliconepolymer SA 100S (manufactured by Kaneka Corporation: trade name “SA100S”) as the component (E), that is, the organic polymer containing acrosslinkable silyl group, an XG-4010 (manufactured by TOAGOSEI CO.,LTD.) as the component (F), that is, the (meth)acrylic polymercontaining an epoxy group, ground calcium carbonate, surface-treatedcalcium carbonate, an antioxidant, a NEOSTAN U-28 (manufactured by NITTOKASEI CO., LTD.) as the component (G), that is, the divalent tin organiccarboxylate, and a FIRMIN 20D (manufactured by KAO CORPORATION) as thecomponent (H), that is, the organic amine compound were loaded, wherebya curing composition was prepared.

TABLE 5 Comparative Blended Example No. Example No. Component substances13 14 15 16 17 5 6 7 8 (E) Acrylic polymer 100 50 — — — — — — —containing crosslinkable silyl group at terminal*²¹ Acrylic polymer — —100 — — — — — — containing crosslinkable silyl group*²² Polyoxyalkylene— 50 — 100 — 100 100 100 100 polymer containing crosslinkable silylgroup*²³ Acrylic-modified — — — — 100 — — — — polyoxyalkylene polymercontaining crosslinkable silyl group*²⁴ (F) Acrylic polymer 60 60 60 6060 — — — 60 containing glycidyl group*²⁵ Epoxy based — — — — — 60 — — —plasticizer*²⁶ Phthalic acid — — — — — — 60 — — based plasticizer*²⁷Acrylic polymer*²⁸ — — — — — — — 60 — (G) Stannous 4 4 4 4 4 4 4 4 —compound*²⁹ Stannic — — — — — — — — 4 compound*³⁰ (H) Organic amine 1 11 1 1 1 1 1 1 compound*³¹ Ground calcium 75 75 75 75 75 75 75 75 75carbonate*³² Surface-treated 135 135 135 135 135 135 135 135 135 calciumcarbonate*³³ Antioxidant*³⁴ 3 3 3 3 3 3 3 3 3 The amounts of the blendedsubstances in Table 5 are each represented by “part(s) by mass”, and thesymbols *21 to *34 represent the following products: *²¹an acrylicpolymer having a crosslinkable silyl group at a terminal of any one ofits molecules produced by living radical polymerization (manufactured byKaneka Corporation: trade name “SA 100S”); *²²the acrylic polymercontaining a crosslinkable silyl group obtained in Synthesis Example 3;*²³a polyoxyalkylene polymer containing a crosslinkable silyl group(manufactured by Kaneka Corporation: trade name “S-810”); *²⁴anacrylic-modified polyoxyalkylene polymer containing a crosslinkablesilyl group (manufactured by Kaneka Corporation: trade name “S-911”);*²⁵an acrylic polymer containing a glycidyl group (manufactured byTOAGOSEI CO., LTD.: trade name “XG-4010”, average number of epoxy groupsin one molecule 1.4); *²⁶an epoxy based plasticizer (manufactured by NewJapan Chemical Co., ltd.: trade name “SANSOCIZER E-145 or EPS”,molecular weight 410); *²⁷a phthalic acid based plasticizer (DINP) *²⁸anacrylic polymer (no functional group, manufactured by TOAGOSEI CO.,LTD.: trade name “UP-1000”); *²⁹stannous octoate as a stannous compound(manufactured by NITTO KASEI CO., LTD.: trade name “NEOSTAN U-28”);*³⁰dibutyltin laurate as a stannic compound (manufactured by NITTO KASEICO., LTD.: trade name “NEOSTAN U-100”); *³¹laurylamine (manufactured byKAO CORPORATION: trade name “FIRMIN 20D”); *³²ground calcium carbonate(manufactured by BIHOKU FUNKA KOGYO CO., LTD.: trade name “WHITON SB”);*³³surface-treated calcium carbonate (manufactured by MARUO CALCIUM CO.,LTD.: trade name “CALFINE 200”); and *³⁴an antioxidant (manufactured byCiba Specialty Chemicals: trade name “TINUVIN B-75”).

Examples 14 to 17 and Comparative Examples 5 to 8

Curable compositions were each prepared in the same manner as in Example13 except that the blended substances and a ratio at which each of thesubstances was blended were changed as shown in each of Table 5.

Each of the above resultant curable compositions was subjected to thefollowing measurement. Table 6 shows the results.

(1) Restoring Property

An H-shaped test body in accordance with JIS A 1439 was produced, andwas aged under an environment of 23° C. and 50% RH for 7 days, anenvironment of 50° C. for 7 days, and an environment of 90° C. for 14days. After that, the body was left at rest under an environment of 23°C. and 50% RH for 24 hours. The thickness at that time (about 12.00 mm)was defined as an initial thickness. Next, the body was left at restunder an environment of 23° C. and 50% RH for 24 hours while beingelongated so as to be twice as thick as the initial thickness (about24.00 mm) with a predetermined jig. 24 hours after that, the jig wasreleased, and the body was left at rest for 1 hour. After that, thethickness was measured, and restoring property was obtained by using thefollowing equation.

Restoring property (%)=(thickness after elongation−thickness afterrelease)/initial thickness×100

(2) Durability Test

A durability test (durability category 9030) was performed in accordancewith JIS A 1439 (1997) 4. 17. In the durability test, a passing resultwas denoted by ∘, and an unsatisfactory result was denoted by x.

(3) Paint Anti-Staining Property

Conditions for aging of sealing material: under conditions of 23° C. and50% RH for 7 days

Conditions for aging of paint: under conditions of 23° C. and 50% RH for7 days

Evaluation method: the heating of the sealing material was promoted in adryer at 50° C. for 7 days. After that, black silica sand was sprinkledon the paint, and the presence or absence of staining was visuallyobserved on the basis of the extent to which the sand adhered to thepaint. All paints were evaluated as follows: the case where no stainingwas observed was denoted by ∘, and the case where staining was observedin any one of the paints was denoted by x.

Various paints used in the paint anti-staining property test were asshown below.

Paints; Buildec: solvent based acryl, manufactured by DAI NIPPON TORYOCO., LTD.

Vinylose: solvent based vinyl chloride, manufactured by DAI NIPPON TORYOCO., LTD.

Beauron: aqueous acryl, manufactured by DAI NIPPON TORYO CO., LTD.

Odecoat G: aqueous acryl, manufactured by Nippon Paint Co., Ltd.

DAN UNI: aqueous acryl, manufactured by Nippon Paint Co., Ltd.

New Topless Clean: aqueous acrylic silicone, manufactured by SK KAKENCo., Ltd.

Pleasecoat: aqueous acryl, manufactured by SK KAKEN Co., Ltd.

Tilelac U: urethane based, manufactured by Nippon Paint Co., Ltd.

New Softlithin: aqueous acryl, manufactured by SK KAKEN Co., Ltd.

(4) Weather Resistance

A weather resistance test was performed in a sunshine weatherometer, andthe external appearance of each of the curable compositions wasinvestigated 1,000 hours, 2,000 hours, 3,000 hours, and 4,000 hoursafter the initiation of the test. In the results of the weatherresistance test, the symbol ∘ means that no crack is present, the symbolΔ means that a small number of cracks are present, and the symbol xmeans that a large number of cracks are present.

(5) Elongation Rate Test

Each of the resultant curable compositions was subjected to anelongation rate test in the same manner as in Example 1, and its maximumelongation rate was measured.

TABLE 6 Example No. Comparative Example No. 13 14 15 16 17 5 6 7 8Restoring 99.55 97.56 98.33 96.67 96.67 95.00 83.62 81.36 73.85 property(%) Durability ◯ ◯ ◯ ◯ ◯ ◯ X X X Paint ◯ ◯ ◯ ◯ ◯ X X ◯ ◯ anti-stainingproperty Weather resistance test After 1,000 ◯ ◯ ◯ ◯ ◯ Δ Δ ◯ ◯ hoursAfter 2,000 ◯ ◯ ◯ ◯ ◯ X X ◯ ◯ hours After 3,000 ◯ ◯ ◯ ◯ ◯ X X ◯ ◯ hoursAfter 4,000 ◯ ◯ ◯ X Δ X X ◯ ◯ hours Elongation 400 600 140 600 500 600630 600 650 rate [%]

As shown in Table 6, each of the curable compositions of Examples 13 to17 was excellent in weather resistance, paint anti-staining property,and durability, and had extremely good restoring property; each of thecompositions had a restoring property of 95% or more. In particular,each of the curable compositions of Examples 13 and 14 each using a(meth)acrylic polymer having a crosslinkable silyl group at a terminalof any one of its molecules as the component (E) was excellent inrestoring property, durability, and paint anti-staining property, hadextremely high weather resistance, and showed an excellent elongationrate. On the other hand, each of the curable compositions of ComparativeExamples 5 and 6 was poor in paint anti-staining property and weatherresistance. In addition, each of the curable compositions of ComparativeExamples 6 to 8 was poor in restoring property, and failed in thedurability test.

Examples 18 to 30 and Comparative Examples 9 to 17 Synthesis Example 4Synthesis of Acrylic Polymer Having Less than One Crosslinkable SilylGroup in any One of its Molecules

200 g of 2-propanol were charged into a 2 L pressure-resistant autoclaveprovided with a stirring machine. Next, air in the autoclave wasrepeatedly subjected to an operation consisting of deaeration andreplacement with nitrogen three times. After that, the air in theautoclave was deaerated under reduced pressure, and the autoclave washeated to 240° C. At the time of the completion of the temperatureincrease, a mixed liquid composed of 670 g of butyl acrylate, 300 g of2-ethylhexyl acrylate, 30 g of γ-methacryloxypropyltrimethoxysilane, 200g of 2-propanol, and 10 g of di-t-butyl peroxide was supplied into theautoclave at a constant speed, and a reaction was initiated. Theaddition and the reaction were performed over 2 hours, and, 10 minutesafter the completion of the addition, the mixture was cooled to 30° C.,whereby 1,350 g of a polymerization liquid were obtained. The resultantpolymerization liquid was condensed under reduced pressure, whereby thesolvent was removed. An acrylic polymer containing a crosslinkable silylgroup, the polymer having Mw of 1,800, Mn of 4,400, and a silylationrate of 0.22, was obtained.

Example 18

As shown in Table 7, predetermined amounts of the organic polymercontaining at least one crosslinkable silyl group in any one of itsmolecules (I), the organic polymer containing less than onecrosslinkable silyl group in any one of its molecules (J), anantioxidant, calcium carbonate, and a dehydrating agent were loaded, andthe blended substances were mixed and stirred under heat and reducedpressure at 110° C. for 2 hours, whereby the blended substances weredehydrated. Further, the thermally expandable hollow spheres (K), anadhesion imparting agent, and a curing catalyst were added to themixture, and the whole was mixed and stirred under reduced pressure for10 minutes. The resultant was hermetically loaded into a cartridgecoated with aluminum, whereby a curing composition was prepared. Itshould be noted that the stirring machine used in this example was auniversal mixing stirring machine manufactured by Shinagawa MachineryWorks CO., LTD.

TABLE 7 Example No. Component Blended substances 18 19 20 21 22 23 24 2526 27 28 29 30 (I) Acrylic polymer containing crosslinkable 65  35  65 65  65  65  65  65  65  65  — — — silyl group at terminal*⁴¹ Acrylicpolymer containing — — — — — — — — — — 65  — — crosslinkable silylgroup*⁴² Acrylic-modified polyoxyalkylene — — — — — — — — — — — 65  —based polymer containing crosslinkable silyl group*⁴³ Polyoxyalkylenebased polymer — 30  — — — — — — — — — — 65  containing crosslinkablesilyl group*⁴⁴ (J) Acrylic polymer*⁴⁵ 35  35  35  35  35  35  35  35  —— 35  35  35  Acrylic polymer*⁴⁶ — — — — — — — — 35  — — — —Polyoxyalkylene based polymer*⁴⁷ — — — — — — — — — 35  — — — (K)F-50D*⁴⁸ 3 3 — — — 1 — — 1 1 3 1 1 F-30VSD*⁴⁹ — — 3 — — — 1 — — — — — —F-80VSD*⁵⁰ — — — 3 — — — 1 — — — — — F-30D*⁵¹ — — — — 3 — — — — — — — —Calcium carbonate*²² 90  90  90  90  90  90  90  90  90  90  90  90  90 Antioxidant*⁵³ 3 3 3 3 3 3 3 3 3 3 3 3 3 Dehydrating agent*⁵⁴ 3 3 3 3 33 3 3 3 3 3 3 3 Adhesion imparting agent*⁵⁵ 2 2 2 2 2 2 2 2 2 2 2 2 2Curing catalyst*⁵⁶ 2 2 2 2 2 2 2 2 2 2 2 2 2 The amounts of the blendedsubstances in Table 7 are each represented by “mass”, and the symbols*41 to *56 represent the following products: *⁴¹SA 100S (manufactured byKaneka Corporation, acrylic polymer having a crosslinkable silyl groupat a terminal of any one of its molecules produced by living radicalpolymerization); *⁴²the acrylic polymer containing a crosslinkable silylgroup obtained in Synthesis Example 3 (silylation rate 1.1); *⁴³MAX450(manufactured by Kaneka Corporation, acrylic-modified polyoxyalkylenepolymer containing a crosslinkable silyl group); *⁴⁴MS Polymer S303(manufactured by Kaneka Corporation, polyoxyalkylene polymer containinga crosslinkable silyl group); *⁴⁵the acrylic polymer containing acrosslinkable silyl group obtained in Synthesis Example 4 (silylationrate 0.22); *⁴⁶UP-1000 (manufactured by TOAGOSEI CO., LTD., acrylicorganic polymer); *⁴⁷DIOR3000 (manufactured by Mitsui Takeda Chemicals,INC., polyoxypropylene polymer); *⁴⁸Matsumoto Microsphere F-50D(manufactured by Matsumoto Yushi-Seiyaku Co., Ltd, thermally expandablehollow spheres); *⁴⁹Matsumoto Microsphere F-30VSD (manufactured byMatsumoto Yushi-Seiyaku Co., Ltd, thermally expandable hollow spheres);*⁵⁰Matsumoto Microsphere F-80VSD (manufactured by MatsumotoYushi-Seiyaku Co., Ltd, thermally expandable hollow spheres);*⁵¹Matsumoto Microsphere F-30D (manufactured by Matsumoto Yushi-SeiyakuCo., Ltd, thermally expandable hollow spheres); *⁵²HAKUENKA CCR(manufactured by Shiraishi Kogyo Kaisha, Ltd., colloidal calciumcarbonate); *⁵³TINUVIN B75 (manufactured by Ciba Specialty Chemicals);*⁵⁴A-171 (manufactured by Nippon Unicar Company Limited,vinyltrimethoxysilane); *⁵⁵A-1120 (manufactured by Nippon Unicar CompanyLimited, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane); and *⁵⁶No. 918(manufactured by Sankyo Organic Chemicals Co., Ltd., product of areaction between dibutyltin oxide and dioctyl phthalate).

Examples 19 to 30 and Comparative Examples 9 to 18

Curable compositions were each prepared in the same manner as in Example18 except that the blended substances and a ratio at which each of thesubstances was blended were changed as shown in each of Tables 7 and 8.

TABLE 8 Comparative Example No. Component Blended substances 9 10 11 1213 14 15 16 17 (I) Acrylic polymer — — — 65  65  65  65  65  100 containing crosslinkable silyl group at terminal*⁴¹ Acrylic polymer — —65  — — — — — — containing crosslinkable silyl group*⁴² Acrylic-modified— 65  — — — — — — — polyoxyalkylene based polymer containingcrosslinkable silyl group*⁴³ Polyoxyalkylene 65  — — — — — — — — basedpolymer containing crosslinkable silyl group*⁴⁴ (J) Acrylic polymer*⁴⁵35  35  35  35  35  35  35  35  — (K) F-50D*⁴⁸ — — — — — — — 20  3Foaming Ammonium — — — — 50  — — — — agent polyphosphate*⁵⁷ Metalhydrate*⁵⁸ — — — — — 50  — — — Expandable — — — — — — 50  — —graphite*⁵⁹ Calcium carbonate*⁵² 90  90  90  90  90  90  90  90  50 Antioxidant*⁵³ 3 3 3 3 3 3 3 3 3 Dehydrating agent*⁵⁴ 3 3 3 3 3 3 3 3 3Adhesion imparting 2 2 2 2 2 2 2 2 2 agent*⁵⁵ Curing catalyst*⁵⁶ 2 2 2 22 2 2 2 2 The amounts of the blended substances in Table 8 are eachrepresented by “mass”, the symbols *41 to 45, 48, and 52 to 56 each havethe same meaning as that of Table 7, and the symbol *57 and *59represents the following product: *⁵⁷TERRAJU C60 (manufactured by CHISSOCORPORATION, coated ammonium polyphosphate); *⁵⁸HIGILITE H42M(manufactured by Showa Denko K.K., aluminum hydroxide); and *⁵⁹GRAFGUARD 220-50N (manufactured by TOMOE Engineering Co., Ltd.).

Each of the above resultant curable compositions was evaluated asdescribed below. Tables 9 and 10 show the results.

(1) Fire Resistance

An abutting test body having a joint length of 50 mm, a joint width of10 mm, and a joint depth of 6 mm is produced by using each of theresultant curable compositions and a ceramic siding material (MOEN Mmanufactured by NICHIHA CORPORATION). It should be noted that the bodyis aged under standard conditions of 23° C. and 50% RH for 14 days.

The test body is exposed to flame from a Bunsen gas burner, the flamehaving a height adjusted to 40 mm, in such a manner that the lowerportion of the joint of the test body has a height of 20 mm from theuppermost portion of the Bunsen burner. The temperature of the backsurface of the joint portion is measured 30 minutes and 60 minutes afterthe initiation of the exposure, and the test body is evaluated for itsfire resistance on the basis of the following criteria:

⊚: lower than 140° C.;

∘: 140° C. or higher and lower than 160° C.;

Δ: 160° C. or higher and lower than 200° C.; and

x: 200° C. or higher.

(2) State of the Rubber-Like Elastic Body on the Back Surface

The state of the rubber-like elastic body on the back surface of thejoint portion 60 minutes after the above fire resistance test wasevaluated by a finger touch and visual observation on the basis of thefollowing criteria:

⊚: a considerable amount of the rubber-like elastic body remains;∘: a small amount of the rubber-like elastic body remains;Δ: no rubber-like elastic body remains, and the back surface becomes ahard film; andx: the joint itself falls within 60 minutes, and does not remain.

(3) Hardness

A test body is produced in the same manner as in the above fireresistance test, and the hardness of the cured curable composition ismeasured with a rubber hardness meter (JIS A type).

(4) Physical Property Retentivity

An abutting test body was produced in the same manner as in the abovefire resistance test by using each of: a composition before the additionof the component (K) or a foaming agent of each of the resultant curablecompositions [Composition Before Addition]; and each of the resultantcurable compositions [composition after the addition of the component(K) or a foaming agent, Composition After Addition]. It should be notedthat each body was aged under standard conditions of 23° C. and 50% RHfor 14 days. Each of the test bodies was subjected to a tensile strengthtest at a tension speed of 50 mm/min, and its maximum elongation ratewas measured. The maximum elongation rates of Composition BeforeAddition and Composition After Addition were compared, and a physicalproperty retentivity (%) was determined. Each of the compositions wasevaluated for its physical property retentivity on the basis of thefollowing criteria:

∘: the physical property retentivity is 50% or more; andx: the physical property retentivity is less than 50%.

(5) Color Tone

Each of the resultant curable compositions was mixed and kneaded with apigment so as to be provided with a color tone. Each of the compositionswas evaluated for its color tone on the basis of the following criteria:

∘: a composition can be provided with an arbitrary color tone; andx: a composition cannot be provided with an arbitrary color tone.

(6) Elongation Rate Test

Each of the resultant curable compositions was subjected to anelongation rate test in the same manner as in Example 1, and its maximumelongation rate was measured.

TABLE 9 Example No. 18 19 20 21 22 23 24 25 26 27 28 29 30 Fire After 30⊚ ⊚ ⊚ ⊚ ⊚ ◯ ◯ ◯ ◯ ◯ ⊚ Δ Δ resistance minutes After 60 ⊚ ◯ ⊚ ⊚ ⊚ ◯ ◯ ◯ ◯◯ ⊚ Δ X minutes State of ⊚ ⊚ ⊚ ⊚ ⊚ ◯ ◯ ◯ ◯ Δ ⊚ Δ X rubber-like elasticbody on back surface of joint Hardness  12  11  12  12  12  12  12  12 12  12  15  25  10 Physical ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ propertyretentivity Color tone ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Elongation 410 410 410410 410 430 430 430 360 360 160 250 300 rate [%]

TABLE 10 Comparative Example No. 9 10 11 12 13 14 15 16 17 Fireresistance After 30 X Δ Δ Δ ◯ Δ ◯ X X minutes After 60 X X Δ Δ ◯ Δ ◯ X Xminutes State ofrubber-like X X Δ Δ ◯ Δ Δ X X elastic body on backsurface of joint Hardness Physical  10  25  15  12  25  25  25  16  50property retentivity — — — — X X X X ◯ Color tone ◯ ◯ ◯ ◯ ◯ ◯ X ◯ ◯Elongationrate [%] 310 260 170 440 180 200 150 200 200

As shown in Tables 9 and 10, each of the curable compositions ofExamples 18 to 30 had fire resistance, and showed a good physicalproperty retentivity and a good color tone. Each of the curablecompositions of Examples 18 to 26 and 28 each using an acrylic polymeras each of the components (I) and (J) showed particularly excellent fireresistance, and the state of a rubber-like elastic body made of each ofthe curable compositions on the back surface of a joint was extremelygood. Further, each of the curable compositions of Examples 18 to 27each using a (meth)acrylic polymer having a crosslinkable silyl group ata terminal of any one of its molecules as the component (I) not only hadfire resistance but also showed a high elongation rate particularlyuseful in a sealing material. On the other hand, each of the curablecomposition of Comparative Example 9 not blended with the component (K)and the curable composition of Comparative Example 16 blended with alarge amount of the component (K) could not obtain fire resistance, andshowed a poor physical property retentivity. The curable composition ofComparative Example 17 not blended with the component (J) could notobtain fire resistance. In addition, each of the curable compositions ofComparative Examples 2 to 7 was also poor in physical propertyretentivity.

Comparative Example 18

A composition was prepared in the same manner as in Example 23 exceptthat the component (I) was not blended. However, the resultantcomposition did not cure.

1. A curable composition excellent in weather resistance, comprising:(A) an organic polymer containing a crosslinkable silyl group; (B) anultraviolet ray absorbing agent having a triazine skeleton; and (C) ahindered amine based light stabilizer.
 2. A curable compositionaccording to claim 1, wherein the component (A) comprises one or morekinds of compounds selected from the group consisting of apolyoxyalkylene based polymer containing a crosslinkable silyl group, a(meth)acrylic-modified polyoxyalkylene based polymer containing acrosslinkable silyl group, and a (meth)acrylic polymer containing acrosslinkable silyl group.
 3. A curable composition according to claim1, wherein the component (A) comprises a (meth)acrylic polymer having acrosslinkable silyl group at a terminal of its molecular chain.
 4. Acurable composition according to claim 3, wherein the component (A)comprises a (meth)acrylic polymer produced by a living radicalpolymerization method.
 5. A curable composition according to claim 3,wherein the component (A) comprises a (meth)acrylic polymer produced byan atom transfer radical polymerization method.
 6. A curable compositionaccording to claim 1, wherein the component (A) comprises a mixture of a(meth)acrylic polymer having a crosslinkable silyl group at a terminalof its molecular chain and a polyoxyalkylene based polymer containing acrosslinkable silyl group.
 7. A curable composition according to claim1, further comprising (D) a compound that reacts with water to producean amine compound.
 8. A curable composition according to claim 1,wherein the component (C) comprises a hindered amine based compoundhaving a triazine skeleton or a hindered amine based compound free of atriazine skeleton.
 9. A curable composition according to claim 1,wherein the component (C) comprises a mixture of a hindered amine basedcompound having a triazine skeleton and a hindered amine based compoundfree of a triazine skeleton.
 10. A sealing material excellent in weatherresistance, comprising the curable composition according to claim 1 asan available ingredient.
 11. A curable composition, comprising: (E) anorganic polymer containing a crosslinkable silyl group; (F) a(meth)acrylic polymer containing an epoxy group; (G) a divalent tinorganic carboxylate; and (H) an organic amine compound.
 12. A curablecomposition according to claim 11, wherein the component (E) comprises a(meth)acrylic polymer having a crosslinkable silyl group at a terminalof its molecular chain.
 13. A curable composition according to claim 12,wherein the component (E) comprises a (meth)acrylic polymer produced bya living radical polymerization method.
 14. A curable compositionaccording to claim 12, wherein the component (E) comprises a(meth)acrylic polymer produced by an atom transfer radicalpolymerization method.
 15. A curable composition according to claim 11,wherein the component (E) comprises a mixture of a (meth)acrylic polymerhaving a crosslinkable silyl group at a terminal of its molecular chainand a polyoxyalkylene based polymer containing a crosslinkable silylgroup.
 16. A curable composition according to claim 11, wherein thecomponent (F) has a weight average molecular weight of 1,000 or more to7,500 or less.
 17. A sealing material, comprising the curablecomposition according to claim 11 as an available ingredient.
 18. Acurable composition having fire resistance, comprising: (I) a reactiveorganic polymer containing at least one crosslinkable silyl group in anyone of its molecules; (J) a reactive organic polymer containing lessthan one crosslinkable silyl group in any one of its molecules; and (K)thermally expandable hollow spheres as essential components, wherein thecurable composition contains the component (K) in an amount of 0.01 partby weight or more to less than 20 parts by weight with respect to atotal of 100 parts by weight of the components (I) and (J).
 19. Acurable composition according to claim 18, wherein the component (I)comprises a (meth)acrylic polymer.
 20. A curable composition accordingto claim 18, wherein the component (I) comprises a (meth)acrylic polymerhaving a crosslinkable silyl group at a terminal of its molecular chain.21. A curable composition according to claim 20, wherein the component(I) comprises a (meth)acrylic polymer produced by a living radicalpolymerization method.
 22. A curable composition according to claim 20,wherein the component (I) comprises a (meth)acrylic polymer produced byan atom transfer radical polymerization method.
 23. A curablecomposition according to claim 18, wherein the component (I) comprises amixture of a (meth)acrylic polymer having a crosslinkable silyl group ata terminal of its molecular chain and a polyoxyalkylene based polymercontaining a crosslinkable silyl group.
 24. A curable compositionaccording to claim 18, wherein the component (J) comprises a(meth)acrylic polymer.
 25. A curable composition according to claim 18,wherein the component (J) has a weight average molecular weight of 2,000to 50,000.
 26. A curable composition according to claim 18, wherein thecurable composition contains the component (J) in an amount of 10 to 300parts by weight with respect to 100 parts by weight of the component(I).
 27. A curable composition according to claim 18, wherein thecurable composition has a hardness of 40 or less after its curing.
 28. Asealing material having fire resistance, comprising the curablecomposition according to claim 18 as an available ingredient.
 29. Amethod of forming a fire-resistant structure, comprising using a wallmaterial having fire resistance and the sealing material having fireresistance according to claim 28.